Soil disease-controlling imides

ABSTRACT

A soil disease controlling agent for preventing and controlling diseases caused by pathogenic fungi living in soil, which comprises an effective amount of at least one of a 2-cycloalkenylamine derivative and its salts as an active ingredient, and at least one inert carrier or diluent.

The present invention relates to a 2-cycloalkenylamine derivative andits salt which are soil disease-controlling agents, and productionthereof. The 2-cycloalkenylamine derivative and its salt which are theactive ingredient of the present invention, have excellent controllingeffect against soil diseases caused by plant pathogens. Moreparticularly, the present invention relates to a soildisease-controlling agent containing as an active ingredient a2-cycloalkenylamine derivative or its salt (hereinafter referred to aspresent compound), a novel 2-cycloalkenylamine derivative and its salt,and production thereof, said 2-cycloalkenylamine derivative beingrepresented by the formula (I), ##STR1## wherein R¹ represents ahydrogen atom, a hydroxyl, amino, lower cycloalkyl, lower cycloalkenyl,lower alkynyl, tetrahydrofurfuryl, piperidyl, arylthio, arylcarboxyl oraryl group, a lower alkyl group which may be substituted with a halogenatom or a cyano, nitro, hydroxyl, lower alkoxyl, lower cycloalkyl, aryl,carboxyl, lower alkoxycarbonyl, lower alkenyloxycarbonyl,aryloxycarbonyl, lower alkylcarbonyl or dialkylamino group, a loweralkenyl group which may be substituted with a halogen atom or an arylgroup, or a lower alkoxyl group which may be substituted with an arylgroup, R² represents a hydrogen atom, a hydroxyl, amino, lowercycloalkyl, lower cycloalkenyl, lower alkynyl, tetrahydrofurfuryl,piperidyl, arylthio, arylcarboxyl or aryl group, a lower alkyl groupwhich may be substituted with a halogen atom or a cyano, nitro,hydroxyl, lower alkoxyl, lower cycloalkyl, aryl, carboxyl, loweralkoxycarbonyl, lower alkenyloxycarbonyl, aryloxycarbonyl, loweralkylcarbonyl or dialkylamino group, a lower alkenyl group which may besubstituted with a halogen atom or an aryl group, a lower alkoxyl groupwhich may be substituted with an aryl group, or a group represented bythe formula, ##STR2## wherein R³ represents a hydrogen atom, a loweralkynyl, cycloalkyl, cycloalkenyl, aryl, lower alkyl-substitutedoxathiinyl, uracilyl, arylcarbonyl or benzdioxanyl group, an alkyl groupwhich may be substituted with a halogen atom or a lower alkoxyl,cycloalkoxyl, aryl, aryloxy, arylthio, cyano, carboxyl or loweralkoxycarbonyl group, or a lower alkenyl group which may be substitutedwith a halogen atom or a carboxyl, lower alkoxyl or alkoxycarbonylgroup, and X represents an oxygen or sulfur atom or an imino group, orR³ and R¹, taken together, may form a lower alkylene or o-phenylenegroup, or R¹ and R², taken together, may form an alkylene or alkenylenegroup which may contain an oxygen or sulfur atom, a carbonyl group or animino group or at least one of substituents, a group represented by theformula, ##STR3## wherein X and Y, which may be the same or different,represent an oxygen or sulfur atom or an imino group, and Z represents acycloalkylene, cycloalkenylene, bicycloalkylene or arylene group, alower alkylene group which may be substituted with a hydroxyl, loweralkoxyl, aryl, lower alkylcarbonyloxy, methylene, alkylidene, mercapto,arylcarbamoyloxy which may be substituted, or lower alkylcarbonylthiogroup, a lower alkenylene group which may be substituted with a halogenatom or a carboxyl or aryl group, or a substituent represented by theformula --A--R-- (in which A represents an oxygen or sulfur atom or animino group, and R represents a lower alkylene group), or a substitutedalkylidene group represented by the formula, ##STR4## wherein R⁴ and R⁵,which may be the same or different, represent a hydrogen atom, a nitro,lower cycloalkyl, aryl, dihydropyranyl, carboxyl or acyl group, a loweralkyl group which may be substituted with a halogen atom or a hydroxyl,lower alkoxyl, aryloxy, lower alkoxycarbonyl, di-lower alkylamino, acylor aryl group, a lower alkenyl group which may be substituted with ahalogen atom or a hydroxyl or aryl group, or a lower alkynyl group whichmay be substituted with an aryl group, or R⁴ and R⁵, taken together, mayform an alkylene or alkenylene group which may contain an oxygen orsulfur atom, a carbonyl group or an imino group, and n represents 1, 2,3 or 4.

The present inventors made an extensive study on controlling agents forsoil diseases, one of the plant diseases which are most difficult tocontrol, and as a result, found that the present compound has excellentcontrolling effect on soil diseases caused by many plant pathogens.

In the plant pathogens on which the present compound has excellentcontrolling effect, there are included pathogens belonging to genusFusarium such as Fusarium oxysporum f. sp. licopersici (fusarium wilt oftomato), Fusarium oxysporum f. sp. raphani (yellows of Japanese radish),Fusarium oxysporum f. sp. cucumerinum (fusarium wilt of cucumber),Fusarium oxysporum f. sp. niveum (fusarium wilt of watermelon), Fusariumoxysporum f. sp. conglutinans (yellows of cabbage), Fusarium oxysporumf. sp. fragariae (yellows of strawberry), Fusarium nivale f. sp.graminicola (fusarium snow blight of wheat), Fusarium roseum f. sp.cerealis (fusarium blight of wheat), Fusarium solani f. sp. pisi (rootrot of pea) and Fusarium oxysporum f. sp. vasinfectum (fusarium wilt ofcotton), pathogens belonging to genus Pythium such as Pythiumaphanidermatum (damping-off of cucumber) and Pythium debaryanum(damping-off of tobacco), pathogens belonging to genus Rhizoctonia suchas Rhizoctonia solani (damping-off of cucumber, black scurf of potato,root rot of sugar beet, rhizoctonia rot of zoysia grass, sore shin oftobacco), Rhizoctonia candida (damping-off of sugar beet) andRhizoctonia bataticola (charcoal rot of soybean), pathogens belonging togenus Verticillium such as Verticillium alboatrum (verticillium wilt ofeggplant and verticillium wilt of chinese cabbage) and Verticilliumdahliae (verticillium wilt of udo), pathogens belonging to genusCorticium such as Corticium rolfsii (southern blight of kidney bean),pathogens belonging to genus Typhula such as Typhula incarnata andTyphula ishikariensis (typhula snow blight of wheat, typhula snow blightof alfalfa) and pathogens belonging to genus Plasmodiophora such asPlasmodiophora brassicae (clubroot of chinese cabbage, clubroot ofcabbage), and the like.

The present compound, therefore, can be used as the active ingredient ofsoil disease-controlling agents for plowland, paddy field, orchard, teagarden, mulberry field, pasture, turf and the like.

In the foregoing formula (I) representing the present compound, the arylgroup includes for example a phenyl, naphthyl, biphenyl, imidazolyl,triazolyl, pyrazolyl, thiazolyl, benzothiazolyl, triazinyl, pyrazinyl,pyrimidyl, uracilyl, furyl, pyridyl, quinolyl, pyrrolyl, quinoxalyl,benzimidazolyl, benzofuryl and thienyl groups, all of which may have asubstituent. Specifically, there are given for example a phenyl,halogen-substituted phenyl, lower alkylphenyl, lower alkenylphenyl,lower haloalkylphenyl, nitrophenyl, cyanophenyl, carboxyphenyl,naphthyl, lower thioalkoxyphenyl, lower alkoxyphenyl, hydroxyphenyl,biphenyl, aryloxyphenyl, aryl-substituted alkoxyphenyl, formylphenyl,hydroxynaphthyl, nitronaphthyl, halobiphenyl, quinoxalyl, thienyl, loweralkylthienyl, lower alkoxycarbonylphenyl, benzoylphenyl,aryl-substituted lower alkoxyphenyl, di-lower alkylaminophenyl, loweracylaminophenyl, lower acylphenyl, imidazolyl, triazolyl,carbamoylphenyl, arylazophenyl, pyrazolyl, arylpyrazolyl, thiazolyl,benzothiazolyl, halothiazolyl, nitrothiazolyl, lower alkylthiazolyl,lower haloalkylthiazolyl, lower alkylbenzothiazolyl, arylthiazolyl,lower alkoxybenzothiazolyl, arylsulfonylthiazolyl, triazinyl,halotriazinyl, lower alkyltriazinyl, lower cycloalkenylaminotriazinyl,pyrazinyl, carboxypyrazinyl, pyrimidyl, halopyrimidyl, loweralkylpyrimidyl, halogenated lower alkylpyrimidyl, hydroxypyrimidyl,lower alkylthiopyrimidyl, uracilyl, furyl, benzofuryl, loweralkylbenzofuryl, lower alkylfuryl, lower haloalkylpyridyl, halopyridyl,lower alkylpyridyl, aryl lower alkoxypyridyl, hydroxypyridyl,nitropyridyl, pyridyl, lower alkylquinolyl, quinolyl, loweralkoxyquinolyl, pyrrolyl and N-lower alkylpyrrolyl groups, and the like.

In the foregoing formula (I) representing the present compound, thearylene group includes for example an o-phenylene and naphthylene groupsand groups described below, all of which may be substituted with ahalogen atom or a nitro or carboxyl group: ##STR5##

Next, a method for producing the present compound will be illustrated.

Method (a):

When the present compound is an amine compound represented by theformula (II), ##STR6## wherein R⁶ represents a hydrogen atom, ahydroxyl, amino, lower alkynyl, tetrahydrofurfuryl, piperidyl, arylthio,arylcarboxyl or aryl group, a lower alkyl group which is substitutedwith a halogen atom or a cyano, nitro, lower alkoxyl, carboxyl, loweralkoxycarbonyl, lower alkenyloxycarbonyl, aryloxycarbonyl, loweralkylcarbonyl or dialkylamino group, a lower alkenyl group which issubstituted with a halogen atom or an aryl group, or a lower alkoxylgroup which may be substituted with an aryl group, R⁸ represents a loweralkynyl, tetrahydrofurfuryl, piperidyl, arylcarboxyl or arylthio group,a lower alkyl group which is substituted with a halogen atom or a cyano,nitro, lower alkoxyl, carboxyl, lower alkoxycarbonyl, loweralkenyloxycarbonyl, lower alkylcarbonyl, dialkylamino or aryloxycarbonylgroup, a lower alkenyl group which is substituted with a halogen atom oran aryl group, or a lower alkoxyl group which may be substituted with anaryl group, and n represents the same meaning as above, it can beproduced, for example, by reacting a compound represented by the formula(III), ##STR7## wherein R⁶ and n represent the same meanings as above,with the equivalent of a compound represented by the formula (IV),

    L-R.sup.8                                                  (IV)

wherein R⁸ represents the same meaning as above, and L represents ahalogen atom, an arylcarboxyl, hydroxyl or lower alkylsulfonyloxy group,or a benzenesulfonyloxy group which may be substituted with a loweralkyl group, at 0° to 150° C. for 1 to 24 hours with or without asolvent in the presence or absence of the equivalent of an acid-bindingagent.

As the compound represented by the formula (IV), there are given forexample methyl iodide, ethyl iodide, 1-bromopropane, 2-bromopropane,1-bromobutane, 1-bromo-2-methylpropane, 1-bromopentane,1-bromo-3-methylbutane, 1-iodohexane, 1-bromoheptane,2-bromo-5-ethylnonane, 3-bromopropionitrile, cyclopropylmethyl bromide,cyclohexyl bromide, 1-bromo-4-methylcyclohexane, cyclohexylmethylbromide, 2,3,5-trimethylcyclohexylmethyl bromide, cyclopentyl bromide,tert-butyl bromide, cyclopropyl bromide, dibromomethane, diiodomethane,bromochloromethane, chlorodifluoromethane, bromotrichloromethane,tribromomethane, tetrabromomethane, 1-bromo-2-chloroethane,1,2-dibromoethane, 1,1,1-trichloroethane, pentachloroethane,hexachloroethane, 1,1-dibromoethane, ethylene chlorohydrin,2,2-dibromoethane, ethylene bromohydrin, 2,2-dichloroethanol,2,2,2-trifluoroethanol, 1,2-dibromopropane, 1,3-dibromopropane,1-bromo-3-chloropropane, 1,2,3-tribromopropane, 1,2-dibromobutane,1,4-dibromobutane, 2,3-dibromobutane, 1-bromo-3-chloro-2-methylpropane,1,5-dibromopentane, 1,6-dibromohexane, 1,3-dibromobutane,2-iodo-1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane,1,1-dichloroethane, allyl bromide, 3-bromocycloheptene,3-bromocyclooctene, 3-bromocyclohexene, 3-bromocyclopentene, propargylbromide, methallyl chloride, 1-chloro-2-butene, 3-chloro-1-butene,4-bromo-1-butene, 3-hexenyl bromide, 1,3-dichloro-1-propene,2,3-dichloro-1-propene, 1,2,3-trichloropropene, 1,3-dichloro-2-butene,1,4-dichloro-2-butene, cinnamyl chloride,bicyclo[2.2.1]-3-methylheptenylmethyl bromide, benzyl bromide,p-chlorobenzyl chloride, m-bromobenzyl bromide, o-fluorobenzyl bromide,2,4-dichlorobenzyl chloride, p-methylbenzyl chloride, p-ethylbenzylchloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl bromide,vinylbenzyl chloride, 2,5-dimethylbenzyl chloride,m-trifluoromethylbenzyl chloride, m-nitrobenzyl bromide, m-cyanobenzylbromide, α,α'-dichloro-p-xylene, α,α'-dibromo-o-xylene,α-chloroethylbenzene, p-bromomethylbenzoic acid, phenethyl bromide,p-nitrophenethyl bromide, β-bromopropylbenzene, β-bromoisopropylbenzene,α,β-dibromoethylbenzene, diphenylmethyl bromide, triphenylmethylbromide, 2-chloro-4-nitrobenzyl chloride, 1-chloromethylnaphthalene,p-methoxybenzyl chloride, p-methylphenyl-n-butyl bromide,2,4-dimethylphenethyl bromide, phenyl-n-butyl bromide, phenyl-n-propylbromide, ethyl bromoacetate, methyl bromoacetate, isopropylchloroacetate, n-butyl chloroacetate, phenyl chloroacetate, allylchloroacetate, vinyl chloroacetate, methyl 2-chloropropionate, ethyl2-bromopropionate, ethyl 2-bromopropionate, ethyl 2-bromobutyrate, ethyl2-bromoisobutyrate, lactonitrile, hydroxyacetonitrile, acetonecyanhydrin, 2,6-dichloro-4-methylpyrimidine, 4-bromobutyronitrile,5-bromovaleronitrile, 2-chloropropionitrile, chloroacetonitrile,bromoacetic acid, 2-chloropropionic acid, 2-bromo-n-butyric acid,α-bromoisobutyric acid, 2-bromoisovaleric acid, cyanuric chloride,6-chloro-3-trifluoromethylpyridine,5,6-dichloro-3-trifluoromethylpyridine, diethyl chlorosuccinate,1,3-cyclohexanedione, phenylsulfenyl bromide,2-methoxycarbonylphenylsulfenyl bromide, bromoacetone, benzoyl peroxide,2-bromomethylbicyclo[2.2.1]heptane and the like.

Method (b):

When the present compound is an amine compound represented by theformula (V), ##STR8## wherein R⁶ and n represent the same meanings asabove, and R⁷ represents a hydrogen atom, a hydroxyl, amino, loweralkynyl, tetrahydrofurfuryl, piperidyl, arylthio or arylcarboxyl group,a lower alkyl group which is substituted with a halogen atom or a cyano,nitro, lower alkoxyl, carboxyl, lower alkoxycarbonyl, loweralkenyloxycarbonyl, aryloxycarbonyl, lower alkylcarbonyl or dialkylaminogroup, a lower alkenyl group which is substituted with a halogen atom oran aryl group, or a lower alkoxyl group which may be substituted with anaryl group, or R⁶ and R⁷, taken together, may form alkylene oralkenylene tributylamine, N-methylmorpholine, etc., acid amides such asformamide, N,N-dimethylformamide, acetamide, etc., sulfur compounds suchas dimethyl sulfoxide, sulfolane, etc., and mixtures thereof. Also, theacid-binding agent includes for example organic bases such as pyridine,triethylamine, N,N-diethylaniline, etc., and inorganic bases such assodium carbonate, potassium carbonate, sodium hydroxide, etc. Aftercompletion of the reaction, the reaction solution is after-treated asusual, and if necessary, the product obtained is purified bychromatography, distillation, recrystallization and the like.

Next, examples of production of the present compound by the methods (c)to (g) will be shown.

Production example 4

To a mixture of 2-cycloheptenylamine (1.11 g, 10 mmoles), triethylamine(1.01 g, 10 mmoles) and chloroform (10 ml), propionyl chloride (0.93 g,10 mmoles) was added dropwise at 0° to 5° C. After stirring at 20° C.for 3 hours, the reaction mixture was poured into a 1N hydrochloricacid, and the separated organic layer was washed with a saturatedaqueous sodium chloride solution and concentrated to obtain 1.50 g ofN-(2-cycloheptenyl)propionamide [Compound (51)].

m.p. 84° C.

Production example 5

To a chloroform (50 ml) solution of succinic anhydride group which maycontain an oxygen or sulfur atom, a carbonyl group, an imino group or atleast one of substituents provided that a case wherein R⁶ and R⁷ are ahydrogen atom at the same time is excluded, it can be produced, forexample, by reacting an amine represented by the formula (VI), ##STR9##wherein R⁶ and R⁷ represent the same meanings as above, with 0.5 to 1equivalent of a compound represented by the formula (VII), ##STR10##wherein n represents the same meaning as above, and E represents ahalogen atom, a lower alkylsulfonyloxy group or a benzenesulfonyloxygroup which may be substituted with a lower alkyl group, with or withouta solvent for 1 to 24 hours in the presence or absence of not less thanthe equivalent of an acid-binding agent.

As the compound represented by the formula (VI), there are given forexample hydrazine, methylamine, ethylamine, n-propylamine,isopropylamine, n-amylamine, 2-ethylhexylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, 2-methylallylamine,3-cyclohexenylamine, allylamine, vinylamine, isoamylamine,neopentylamine, 1,2-dimethylpropylamine, n-hexylamine, n-heptylamine,2-methylpentylamine, 1,3,3-tetramethylbutylamine, cyclopropylamine,cyclopentylamine, 3-methylcyclohexylamine, cyclohexylamine,1,1-dimethylpropargylamine, 1,1-diethylpropargylamine,ethylpropargylamine, 2-chloroethylamine, 2-bromoethylamine,3-bromopropylamine, 2,2,2-trifluoroethylamine, 2-methoxyethylamine,2-ethoxyethylamine, aminoacetaldehyde dimethyl acetal, aminoacetaldehydediethyl acetal, 3-methoxypropylamine, 3-ethoxypropylamine,3-isopropoxypropylamine, butoxypropylamine, isobutoxypropylamine,2-ethylhexyloxypropylamine, β-aminopropionitrile,cyclopropylmethylamine, cyclohexylmethylamine,N-(2-ethylhexyl)-2-cyclopentenylamine, dimethylamine, diethylamine,di-n-propylamine, di-(2-ethylhexyl)amine, N-methylcyclohexylamine,diallylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine,di-n-amylamine, diisoamylamine, di-n-hexylamine, dicyclohexylamine,N-methylpropargylamine, N-ethyl-n-butylamine, N-methyl-β-alanylnitrile,β-aminoethanol, diisopropanolamine, isopropylcyclohexylamine,diisopropylamine, ethylbutylamine, N-(2-chloroethyl)methylamine,N-methylethanolamine, 2-ethylaminoethanol, 2-isopropylaminoethanol,2-tert-butylaminoethanol, diethanolamine,N-(β-hydroxyethyl)-2-cyclopentenylamine, tris(oxymethyl)aminomethane,1-hydroxyethylamine, 3-amino-1-prpanol, 2-amino-1-propanol,1-amino-2-propanol, 2-amino-1-butanol, diglycolamine,5-amino-1-pentanol, 6-amino-1-hexanol, 3-amino-1,2-propanediol,1-aminomethyl-1-cyclohexanol, N-phenylethanolamine,2-benzylamino-1-propanol, N-n-butylethanolamine,3-aminomethyl-3,5,5-trimethylcyclohexanol, benzylamine,4-chlorobenzylamine, 4-methoxybenzylamine, 2,4-dichlorobenzylamine,N-methylbenzylamine, dibenzylamine, aminodiphenylmethane,α-methylbenzylamine, N-isopropylbenzylamine,4-hydroxy-3-methoxybenzylamine, m-nitrobenzylamine, 2-methylbenzylamine,α-phenethylamine, phenethylamine, p-chlorophenethylamine,4-bromophenylbutylamine, N-ethylbenzylamine, aniline, o-hydroxyaniline,o-nitroaniline, 3-nitro-4-aminotoluene, 2-chloro-4-nitroaniline,4-methoxy-2-nitroaniline, 2-fluoro-5-nitroaniline,N-methyl-p-nitroaniline, p-n-butylaniline, o-phenylaniline,3,4-dimethylaniline, 2,4,6-trimethylaniline, m-bromoaniline,o-fluoroaniline, 2,5-dichloroaniline, 3,5-dichloroaniline,2,4,5-trichloroaniline, 2-chloro-6-methylaniline,5-chloro-2-hydroxyaniline, 3-methoxy-6-chloroaniline,3-trifluoromethyl-4-chloroaniline, 2-nitro-4-trifluoromethylaniline,4-trifluoromethylaniline, 2-trifluoromethylaniline,4-methoxy-3-trifluoromethylaniline, 2,4-dinitroaniline,2-bromo-4,6-dinitroaniline, 3-cyano-4-chloroaniline, o-methoxyaniline,4-methoxy-2-methylaniline, 2,5-dimethoxyaniline,3,4,5-trimethoxyaniline, 3,4-dimethylenedioxyaniline,6-amino-1,4-benzdioxane, p-phenoxyaniline, 2,4-dibenzyloxyaniline,4-benzyloxyaniline, p-cresidine, N-ethylaniline, N-methoxy-o-toluidine,diphenylamine, N-methyl-p-nitroaniline, N-ethyl-o-toluidine,N-methyl-p-anisidine, N-benzyl-p-anisidine, 8-amino-2-naphthol,4-nitro-1-naphthylamine, 5,6,7,8-tetrahydro-1-naphthylamine,1,2,3,4-tetrahydronaphthylamine, α-naphthylamine,4-(2,4,6-trichlorophenyl)aniline, 4,4'-oxydianiline,3-methylthioaniline, 4-amionbenzonitrile, ethyl m-aminobenzoate,p-aminoazobenzene, 2-aminobenzophenone, 4-aminobenzamide,m-aminoacetophenone, 1,2,4 -triazole, 4-amino-1,2,4-triazole,3-amino-2-phenylpyrazole, 3,5-dimethylpyrazole, 2-aminothiazole,2-aminobenzothiazole, 2-amino-5-chlorothiazole, 2-amino-5-nitrothiazole,2-amino-4-methylthiazole, 2-amino-5,6-dihydro-4H-cyclopentathiazole,2-amino-(4-chloromethyl)thiazole,2-amino-5-(p-nitrophenylsulfonyl)thiazole,2-amino-6-methoxybenzothiazole, 2-amino-6-methylbenzothiazole,2-amino-4-phenylthiazole, benzimidazole, 2-benzimidazole methanol,2-benzyl-2-imidazoline, 2-hydroxybenzimidazole,2-methylthio-2-imidazoline, imidazole,2-(1-naphthylmethyl)-2-imidazoline, 2-ethylimidazole, 2-phenylimidazole,4,5-dicyanoimidazole, 2,4,5-tribromoimidazole,2-methyl-4,5-dicyanoimidazole, 4-nitroimidazole, 5-chlorobenzimidazole,2-(α-hydroxybenzyl)benzimidazole, 3-amino-1,2,4-triazine,3-amino-5,6-dimethyl-1,2,4-triazine, aminopyrazine,3-aminopyrazine-2-carboxylic acid, 2-amino-4,6-dichloropyrimidine,2-aminopyrimidine, 2-amino-6-chloro-4-hydroxypyrimidine,4-amino-6-chloro-2-methylthiopyrimidine, 5-aminouracil, furfurylamine,tetrahydrofurfurylamine, hydroxylamine, N-methylhydroxylamine,O-methylhydroxylamine, O-ethylhydroxylamine, O,N-dimethylhydroxylamine,o-benzyloxyamine, 2-amino-5-bromopyridine, 6-amino-3-picoline,2-amino-3-benzyloxypyridine, 2-amino-3-hydroxypyridine,2-amino-5-nitropyridine, 2-aminopyridine, 2-aminomethylpyridine,1,2,5,6-tetrahydropyridine, 8-amino-6-methylquinoline, 8-aminoquinoline,3,5-diiodo-4-pyridone, 8-amino-6-methoxyquinoline,1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline,N-(3-aminopropyl)morpholine, 2,6-dimethylmorpholine, morpholine,thiomorpholine, 3-acetyl-2,4-dimethylpyrrole, 2,5-dimethylpyrrole,2,5-dimethylpyrrolidine, pyrrole, pyrrolidine, 3-pyrroline, methylpyrrole-2-carboxylate, 3-pyrrolidinol, N-methylpiperazine,1-(o-methoxyphenyl)piperazine, 1-(2-pyridyl)piperazine,N-(α,α,α-trifluoromethyl-m-tolyl)piperazine, ethyleneimine,dodecamethyleneimine, hexamethyleneimine, 3-amino-N-ethylpiperidine,4-amino-1-benzylpiperidine, N-(2-aminoethyl)piperidine,4-bromo-4-phenylpiperidine, 4-(p-chlorophenyl)-4-hydroxypiperidine,4-cyano-4-phenylpiperidine, 2,6-dimethylpiperidine, piperidine,2-piperidine ethanol, 2,2,6,6-tetramethyl-4-piperidone,2,2,6,6-tetramethylpiperidine and the like.

The solvent used in the above methods (a) and (b) includes for examplealiphatic hydrocarbons such as hexane, heptane, ligroin, petroleumether, etc., aromatic hydrocarbons such as benzene, toluene, xylene,etc., halogenated hydrocarbons such as chloroform, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether, etc., nitro compounds such an nitroethane,nitrobenzene, etc., nitriles such as acetonitrile, isobutyronitrile,etc., tertiary amines such as pyridine, triethylamine,N,N-diethylaniline, tributylamine, N-methylmorpholine, etc., acid amidessuch as N,N-dimethylformamide, acetamide, etc., sulfur compounds such asdimethyl sulfoxide, sulfolane, etc., and mixtures thereof.

Also, the acid-binding agent includes for example organic bases such aspyridine, triethylamine, N,N-diethylaniline, etc., and inorganic basessuch as sodium carbonate, potassium carbonate, sodium hydride, etc.

After completion of the reaction, the reaction solution is after-treatedas usual, for example it is poured into water and the organic layer isseparated and concentrated. If necessary, the product obtained ispurified by chromatography, distillation, recrystallization and thelike.

Next, examples of production of the present compound by the methods (a)and (b) will be shown.

Production example 1

To a mixture of 2-cyclohexenylamine (0.97 g, 10 mmoles), triethylamine(1.01 g, 10 mmoles) and chloroform (10 ml) was added dropwise ethylbromoacetate (1.67 g, 10 mmoles) at 0° to 5° C. After completion of theaddition, the resulting mixture was heated under reflux for 3 hours.

Then the reaction solution was after-treated as usual and purified bychromatography to obtain 1.28 g of N-(2-cyclohexenyl)glycine ethyl ester[Compound (1)].

n_(D) ²³.3 1.4711

Production example 2

2-Cycloheptenylamine (1.11 g, 10 mmoles) was added dropwise to a mixtureof an aqueous 50 wt.% hydroxyacetonitrile solution (1.14 g, 10 mmoles)and an aqueous 50% EtOH (10 ml) at 35° to 40° C.

After the resulting mixture was kept at this temperature for 30 minutes,it was after-treated as usual and purified by chromatography to obtain1.35 g of N-(2-cycloheptenyl)glycinonitrile [Compound (2) ].

n_(D) ²⁴.0 1.4950

Production example 3

A mixture of 3-bromocycloheptene (1.75 g, 10 mmoles), triethylamine(1.01 g, 10 mmoles), morpholine (0.87 g, 10 mmoles) and chloroform (10ml) was heated under reflux for 3 hours. After completion of therefluxing, the reaction mixture was after-treated as usual and purifiedby chromatography to obtain 0.91 g of N-(2-cycloheptenyl)morpholine[Compound (3)].

n_(D) ²⁵.2 1.5039

Some of the present compounds which can be produced by these methods areshown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Present compounds represented by the formula,                                  ##STR11##                                                                    Com-                                                                          pound                                                                         No.   R.sup.1                                                                             R.sup.2           n   Physical constant                           ______________________________________                                         (1)  H     CH.sub.2 COOC.sub.2 H.sub.5                                                                     2   n.sub.D.sup..sup.23.3 1.4711                 (2)  H     CH.sub.2 CN       3   n.sub.D.sup.24.0 1.4950                      (3)  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                              3     n.sub.D.sup.25.2 1.5039                        (4)  H     C(CH.sub.3).sub.2 CN                                                                            3   n.sub.D.sup.26.2 1.4791                      (5)  H     CH(CH.sub.3)CN    3   n.sub.D.sup.26.0 1.4813                      (6)  H     CH.sub.2 COOCH.sub.3                                                                            3   n.sub.D.sup.22.2 1.4811                      (7)  H     CH.sub.2 COOC.sub.2 H.sub.5                                                                     3   n.sub.D.sup.22.9 1.4761                      (8)  H                                                                                    ##STR12##        3   n.sub.D.sup.22.0 1.5202                      (9)  H                                                                                    ##STR13##        3   m.p. 105° C.                         (10)  H                                                                                    ##STR14##        3   n.sub.D.sup.25.5 1.4986                     (11)  H                                                                                    ##STR15##        2   n.sub.D.sup.18.8 1.5128                     (12)  H     OCH.sub.3         2   n.sub.D.sup.30.2 1.4680                     (13)  H                                                                                    ##STR16##        3   n.sub.D.sup.26.7 1.5784                     (14)  H                                                                                    ##STR17##        3   n.sub.D.sup.26.6 1.5280                     (15)  H     CH.sub.2 CCH      3   n.sub.D.sup.23.7 1.5030                     (16)  H                                                                                    ##STR18##        3   n.sub.D.sup.22.7 1.5196                     (17)  H     CH(CH.sub.3).sub.2                                                                              3   n.sub.D.sup.24.8 1.4702                     (18)  H     CH.sub.2 COCH.sub.3                                                                             3   n.sub.D.sup.17.2 1.5375                     (19)  H     (CH.sub.2).sub.5 Cl                                                                             3   n.sub.D.sup.23.5 1.4990                     (20) (21)                                                                            ##STR19##          2 3   n.sub.D.sup.24.0 1.6041 n.sub.D.sup.23.9                                      1.5189                                        (22)  H     CH.sub.2 COOH     3   m.p. >300° C.                                                          (dec.)                                      (23)  H     CHCH.sub.3 COOCH.sub.3                                                                          3   n.sub.D.sup.22.3 1.4718                     (24)  H     CH.sub.2 CN       2   n.sub.D.sup.20.1 1.5231                     (25)  H     C.sub.2 H.sub.5   2   n.sub.D.sup.21.6 1.4781                     (26)  H                                                                                    ##STR20##        2   n.sub.D.sup.29.7 1.5330                     (27)  H                                                                                    ##STR21##        2   n.sub.D.sup.30.1 1.4640                     (28)  H     OC.sub.2 H.sub.5  2   n.sub.D.sup.30.1 1.4629                     (29)  H                                                                                    ##STR22##        2   Resinous product                            (30)  H                                                                                    ##STR23##        2   m.p. 82°-84° C.               (31)  H                                                                                    ##STR24##        2   n.sub. D.sup.29.5 1.5170                    (32)  H                                                                                    ##STR25##        2   m.p. 108°-110° C.             (33) (34)                                                                            ##STR26##          2 2   n.sub.D.sup.30.4 1.5165 n.sub.D.sup.26.4                                      1.5142                                        (35)  H                                                                                    ##STR27##        2   m.p. 144° C.                         (36)  H                                                                                    ##STR28##        2   Resinous product                            (37)  H     NH.sub.2          2   n.sub.D.sup.30.0 1.4778                     (38)  H                                                                                    ##STR29##        2   m.p. >300° C.                        (39)  H                                                                                    ##STR30##        2   m.p. 153°-155° C.             (40)  H                                                                                    ##STR31##        2   n.sub.D.sup.24.7 1.5930                     (41)  H                                                                                    ##STR32##        2   n.sub.D.sup.24.2 1.5495                     (42)  H     CH.sub.2 COOCH.sub.3                                                                            2   n.sub.D.sup.18.5 1.4791                     (43)  H     CH(CH.sub.3)COOCH.sub.3                                                                         2   n.sub.D.sup.20.7 1.4694                     (45)  H     CH.sub.2 COOH     2   m.p. -                                            H                                                                                    ##STR33##        2   n.sub.D.sup.17.5                            (46)  H     CHCH.sub.3 CN     2   n.sub.D.sup.17.3 1.4855                     (47)  H     C(CH.sub.3).sub.2 CN                                                                            2   n.sub.D.sup.17.3 1.4796                     (48)  H     CH.sub.2 CN       1   n.sub.D.sup.25.0 1.4819                     (49)  H     CH.sub.2 CN       4   n.sub.D.sup.24.7 1.4921                     (50)  H                                                                                    ##STR34##        3   n.sub.D.sup.25.2 1.5930                     ______________________________________                                    

Method (c):

When the present compound is an acid amide compound represented by theformula (VIII), ##STR35## wherein R³, X and n represent the samemeanings as above, provided that when X is an oxygen atom and R¹ is ahydrogen atom, the following combinations of n and R³ are excluded: n=1and R³ =methyl or phenyl; n=2 and R³ =methyl, propyl, phenyl,chloromethyl, trichloromethyl, tert-butyl or trifluoromethyl; n=3 and R³=methyl or trifluoromethyl; n=4 and R³ =methyl, when X is an oxygenatom, R¹ is benzyl and n is 1, R³ is not methyl, and when X is an iminogroup, R¹ is a hydrogen atom and n is 2, R³ is not a trichloromethylgroup, it can be produced, for example, by reacting a compoundrepresented by the formula (IX), ##STR36## wherein R¹ and n representthe same meanings as above, with 1.0 to 1.1 equivalent of a compoundrepresented by the formula (X), ##STR37## wherein R³ and X represent thesame meanings as above, and M represents a halogen atom, a hydroxyl,lower alkoxyl, mercapto or lower alkylthio group, or a group representedby the formula ##STR38## (in which R³ and X represent the same meaningsas above), at -78° to 200° C. for several minutes to 24 hours in asolvent in the presence or absence of 1.0 to 1.1 equivalent of anacid-binding agent, or by simply heating the both compounds at hightemperatures and removing the formed hydrogen chloride, water, loweralcohol, hydrogen sulfide or lower mercapto.

As the above compound represented by the formula (X), there are givenfor example formic acid, ethyl formate, acetic acid, acetyl chloride,propionic acid, propionyl chloride, 2-methylpropionic acid,2-methylpropionyl chloride, 2,2-dimethylpropionic acid,2,2-dimethylpropionyl chloride, 3,3-dimethylbutanoic acid,3,3-dimethylbutanoyl chloride, myristic acid,2,2,3,3,3-pentafluoropropionic acid, 2,2,3,3,3-pentafluoropropionylchloride, chloroacetyl chloride, trichloroacetyl chloride, chloroaceticacid, trichloroacetic acid, dichloroacetic acid, dichloroacetylchloride, methoxyacetyl chloride, methoxyacetic acid, l-menthoxyaceticacid, l-menthoxyacetyl choride, cyanoacetic acid, cyanoacetyl chloride,methyl cyanoacetate, ethyl cyanoacetate, phenoxyacetic acid,phenoxyacetyl chloride phenylthioacetic acid, phenylthioacetyl chloride,phenylacetic acid, phenylacetyl chloride, o-, m- or p-chlorophenylaceticacid, o-, m- or p-chlorophenylacetyl chloride, α-chlorophenylaceticacid, α-chlorophenylacetyl chloride, crotonic acid, crotonyl chloride,2-phenylpropionic acid, 2-phenylpropionyl chloride, o-, m- orp-tolylacetic acid, o-, m- or p-tolylacetyl chloride, 3-chloropropenoicacid, 3-chloropropenoyl chloride, propargylic acid, methyl propargylate,ethyl propargylate, 2-butynoic acid, ethyl 2-butynoate, 3-butynoic acid,3-butynoyl chloride, methyl 3-butynoate, ethyl 3-butynoate,cyclohexanecarboxylic acid, cyclohexanecarbonyl chloride,cyclobutanecarboxylic acid, cyclobutanecarbonyl chloride,cyclopropanecarboxylic acid, cyclopropanecarbonyl chloride,3-cyclohexenecarboxylic acid, 3-cyclohexenecarbonyl chloride, benzoicacid, benzoyl chloride, o-, m- or p-chlorobenzoic acid, o-, m- orp-chlorobenzoyl chloride, o-, m- or p-methylbenzoic acid, o-, m- orp-methylbenzoyl chloride, salicylic acid, o-, m- or p-methoxybenzoicacid, o-, m- or p-methoxybenzoyl chloride, 2,6-dimethylbenzoic acid,2,6-dimethylbenzoyl chloride, 2,4-dichlorobenzoic acid,2,4-dichlorobenzoyl chloride, o- or m-trifluoromethylbenzoyl chloride,o- or m-trifluoromethylbenzoic acid, p-fluorobenzoic acid,p-fluorobenzoyl chloride, 4-tert-butylthiobenzoic acid, O-ethyl4-tert-butylthiobenzoate, ethyl 4-tert-butyldithiobenzoate, 1-naphthoicacid, 1-naphthoyl chloride, 2- or 3-furoic acid, 2- or 3-furoylchloride, 2,5-dimethyl-3-furoic acid, 2,5-dimethyl-3-furoyl chloride,3-methyl-2-furoic acid, 3-methyl-2-furoyl chloride, isonicotinic acid,isonicotinyl chloride, N-methylpyrrole-2-carboxylic acid,N-methylpyrrole-2-carbonyl chloride, 2-quinoxalinecarbonyl chloride,2-quinoxalinecarboxylic acid, 2-thiophenecarboxylic acid,2-thiophenecarbonyl chloride, 2-benzimidazolecarboxylic acid,3-methyl-5-isoxazolecarboxylic acid, 3-methylisoxazolecarbonyl chloride,2,4-dimethyl-4-oxazolinecarboxylic acid,2,4-dimethyl-4-oxazolinecarbonyl chloride, 2-pyrazinecarboxylic acid,2-pyrazinecarbonyl chloride, 2,4-dihydroxypyrimidine-5-carboxylic acid,1,2,4-triazole-5-carboxylic acid, 1,4-benzdioxane-2-carboxylic acid,1,4-benzdioxane-2-carbonyl chloride, 4-pyrazolecarboxylic acid,5-imidazolecarboxylic acid, 2,3-dihydro-6-methyl-5-oxathiinecarboxylicacid, 2,3-dihydro-6-methyl-5-oxathiinecarbonyl chloride, succinic acid,maleic acid, phthalic acid, itaconic acid, monomethyl succinate,monoethyl maleate, monoethyl phthalate, monoethyl itaconate,tetrachlorophthalic acid, dimethylmaleic acid, monoethyltetrachlorophthalate, monoethyl 2,2-dimethylglutarate, glutaric acid,2,2-dimethylglutaric acid, monoethyl glutarate, monoethyl2,2-dimethylglutarate, 3,3-dimethylglutaric acid, citraconic acid,monoethyl 3,3-dimethylglutarate, monoethyl citraconate,tetrabromophthalic acid, monoethyl tetrabromophthalate, dithioaceticacid, trifluorodithioacetic acid, dithiobenzoic acid, O-ethylthioacetate, O-methyl thiobenzoate, O-methyl p-methoxythiobenzoate,thioacetyl chloride, ethyl dithioacetate, methyl dithioisovalerate,methyl p-chlorodithiobenzoate, methyl p-hydroxydithiobenzoate,o-iodobenzoic acid, o-iodobenzoyl chloride, imidazolylacetic acid,triazolylacetic acid, 3,5-bis(trifluoromethyl)benzoic acid,3,5-bis(trifluoromethyl)benzoyl chloride, 5-chloropentanoyl chloride,diphenylacetyl chloride, 4-chloro-2-methylphenoxyacetic acid,benzoylformyl chloride, 1,4-benzdioxane-6-acetyl chloride,3-chloropropionyl chloride, butanoyl chloride, 3-methylbutanoylchloride, bromoacetyl bromide, isobutoxyacetyl chloride, propenoylchloride, 3-ethoxypropenoyl chloride, cinnamoyl chloride,2-fluorocinnamoyl chloride, m-nitrobenzoyl chloride,2-phenylcyclopropanecarbonyl chloride, 1-methylcyclopropanecarbonylchloride, 2,2,3,3-tetramethylcyclopropanecarbonyl chloride,m-bromobenzoyl chloride, m-cyanobenzoyl chloride, p-dimethylaminobenzoylchloride, m-fluorobenzoyl chloride, 2-chloro-4-nitrobenzoyl chloride,m-fluorobenzoic acid, 2-nitro-3-phenoxybenzoyl chloride,2,2-dimethyl-3-(2,2-dichloroethenyl)cyclopropanecarboxylic acidchloride, nicotinic acid, 3,5-dichlorobenzoyl chloride, nicotinylchloride, pyrrole-2-carbonyl chloride, propyl3-chloroformyl-3-butenoate, pyrrole-2-carboxylic acid,3-methylbenzofuran-2-carboxylic acid chloride, chloroacetimidoylchloride, methyl 3-chloroformylpropanoate, trichloroacetimidic acid andthe like.

Also, as an acid anhydride among the compounds represented by theformula (X), there are given for example anhydrides of the followingcompounds: Acetic acid, propionic acid, 2-methylpropionic acid,2,2-dimethylpropionic acid, 3,3-dimethylbutanoic acid, myristic acid,2,2,3,3-pentafluoropropionic acid, chloroacetic acid, dichloroaceticacid, trichloroacetic acid, methoxyacetic acid, l-menthoxyacetic acid,cyanoacetic acid, phenoxyacetic acid, phenylthioacetic acid,phenylacetic acid, o-, m- or p-chlorophenylacetic acid,α-chlorophenylacetic acid, crotonic acid, 2-phenylpropionic acid, o-, m-or p-tolylacetic acid, 3-chloropropenoic acid, propargylic acid,2-butynoic acid, 3-butynoic acid, cyclohexanecarboxylic acid,cyclobutanecarboxylic acid, cyclopropanecarboxylic acid,3-cyclohexenecarboxylic acid, benzoic acid, o-, m- or p-chlorobenzoicacid, o-, m- or p-methylbenzoic acid, salicylic acid, o-, m- orp-methoxybenzoic acid, 2,6-dimethylbenzoic acid, 2,4-dichlorobenzoicacid, o- or m-trifluoromethylbenzoic acid, p-fluorobenzoic acid,1-naphthoic acid, 2- or 3-furoic acid, 2,5-dimethyl-3-furoic acid,3-methyl-2-furoyl chloride, isonicotinic acid,N-methylpyrrole-2-carboxylic acid, 2-quinoxalinecarboxylic acid,2-thiophenecarboxylic acid, 2-benzimidazolecarboxylic acid,3-methyl-5-isoxazolecarboxylic acid, 2,4-dimethyl-4-oxazolinecarboxylicacid, 2-pyrazinecarboxylic acid, 2,4-dihydroxypyrimidine-5-carboxylicacid, 1,2,4-triazole-5-carboxylic acid, 1,4-benzdioxane-2-carboxylicacid, 4-pyrazolecarboxylic acid, 5-imidazolecarboxylic acid,2,3-dihydro-6-methyl-5-oxathiinecarboxylic acid, n-butyric acid,n-valeric acid, isovaleric acid, lauric acid, caproic acid,trifluoroacetic acid and the like.

Method (d):

When the present compound is an acid amide compound represented by theformula (XI), ##STR39## wherein R⁹ represents a hydrogen atom, ahydroxyl, lower cycloalkyl, lower cycloalkenyl, lower alkynyl,tetrahydrofurfuryl, piperidyl, arylthio, arylcarboxyl or aryl group, alower alkyl group which may be substituted with a halogen atom or acyano, hydroxyl, lower alkoxyl, lower cycloalkyl, aryl, carboxyl, loweralkoxycarbonyl, lower alkenyloxycarbonyl, aryloxycarbonyl, loweralkylcarbonyl or dialkylamino group, a lower alkenyl group which may besubstituted with a halogen atom or an aryl group, or a lower alkoxylgroup which may be substituted with an aryl group, Z' represents acycloalkenylene, cycloalkylene, bicycloalkylene or arylene group, alower alkylene group which may be substituted with a hydroxyl, loweralkoxyl, aryl, lower alkylcarbonyloxy, methylene, alkylidene, mercapto,carbamoyloxy group which may be substituted, or lower alkylcarbonylthiogroup, or a lower alkenylene group which may be substituted with ahalogen atom or a carboxyl or aryl group, and n represents the samemeaning as above, it can be produced, for example, by reacting acompound represented by the formula (XII), ##STR40## wherein R⁹ and nrepresent the same meanings as above, with 1.0 to 1.1 equivalent of acompound represented by the formula (XIII), ##STR41## wherein Z'represents the same meaning as above, at -78° to 200° C. for 1 to 24hours with or without a solvent.

As the compound represented by the formula (XIII), there are given forexample the anhydrides of succinic acid, maleic acid, phthalic acid,itaconic acid, tetrachlorophthalic acid, dimethylmaleic acid, glutaricacid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, citraconicacid, tetrabromophthalic acid, 1,2-cyclohexanedicarboxylic acid,isopropylidenesuccinic acid, 3,4,5,6-tetrahydrophthalic acid, melliticacid, 4-carboxyphthalic acid, dichloromaleic acid, phenylmaleic acid,3-nitrophthalic acid, 1,2-pyridinedicarboxylic acid,3,4-furandicarboxylic acid, 3,4-pyrazinedicarboxylic acid, naphthalicacid, 1,2-cyclobutanedicarboxylic acid, monochloromaleic acid,monobromomaleic acid, dibromomaleic acid, monofluoromaleic acid,difluoromaleic acid, malic acid, thiomalic acid, methoxysuccinic acid,2-methyl-2-phenylsuccinic acid, acetoxysuccinic acid, acetylthiosuccinicacid, tetrafluorophthalic acid, 5-norbornane-2,3-dicarboxylic acid,1,2-dimethyl-1,2-cyclopropanedicarboxylic acid, camphanic acid, diphenicacid, diphenylcarbamoyloxysuccinic acid,cis,cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid and the like.

Method (e):

When the present compound is an acid amide compound represented by theformula (XIV), ##STR42## wherein R¹⁰ represents a lower cycloalkyl,lower cycloalkenyl, arylthio, lower alkynyl, tetrahydrofurfuryl,piperidyl, arylcarboxyl or aryl group, a lower alkyl group which may besubstituted with a halogen atom or a cyano, hydroxyl, lower cycloalkyl,aryl, carboxyl, lower alkoxycarbonyl, lower alkenyloxycarbonyl,aryloxycarbonyl, lower alkylcarbonyl or dialkylamino group, or a loweralkenyl group which may be substituted with a halogen atom or an arylgroup, and R³ and n represent the same meanings as above, it can beproduced by reacting a compound represented by the formula (XV),##STR43## wherein R³, X and n represent the same meanings as above, withnot less than the equivalent of a compound represented by the formula(XVI),

    R.sup.10 --L'                                              (XVI)

wherein R¹⁰ represents the same meaning as above, and L' represents ahalogen atom, an arylcarboxyl or lower alkylsulfonyloxy group, or abenzenesulfonyloxy group which may be substituted with a lower alkylgroup, with or without a solvent at 0° to 150° C. for 1 to 24 hours inthe presence of not less than the equivalent of an acid-binding agent.

Method (f):

When the present compound is represented by the foregoing formula (VIII)(provided that when X is an oxygen atom and R¹ is a hydrogen atom, thefollowing combinations of n and R³ are excluded: n=1 and R³ =methyl orphenyl; n=2 and R³ =methyl, propyl, phenyl, chloromethyl,trichloromethyl, tert-butyl or trifluoromethyl; n=3 and R³ =methyl ortrifluoromethyl; n=4 and R³ =methyl, when X is an oxygen atom, R¹ isbenzyl and n is 1, R³ is not methyl, and when X is an imino group, R¹ isa hydrogen atom and n is 2, R³ is not a trichloromethyl group), it canalso be produced, for example, by reacting a compound represented by theformula (XVII), ##STR44## wherein R¹, R³ and X represent the samemeanings as above, with not less than the equivalent of a compoundrepresented by the foregoing formula (VII) with or without a solvent at0° to 150° C. for 1 to 24 hours in the presence of not less than theequivalent of an acid-binding agent.

As the compound represented by the formula (XVII), there are given forexample formamide, pentan amide, butan amide, N-ethylacetamide,acetamide, chloroacetamide, dichloroacetamide, trichloroacetamide,N-tert-butylacetamide, malonamide, N-methylchloroacetamide,cyanoacetamide, N-(2-hydroxyethyl)acetamide, methacrylamide, lactamide,2,2-dimethylpropan amide, N-methylformamide, trifluoroacetamide,N-ethylformamide, octadecan amide, N-(hydroxymethyl)acrylamide,thioacetamide, propan amide, N-(2-chloroethyl)acetamide,N-methylacetamide, 2-hydroxybenzanilide, acetanilide,2'-hydroxyacetamide, nicotinamide, formanilide, thioisonicotinamide,ω-thiocaprolactam, benzanilide, 5-chloro-2-hydroxybenzanilide,3'-nitroacetanilide, 4'-chloroacetanilide, 3'-chloroacetanilide,4-hydroxybenzamide, 3,5-dinitrobenzamide, 3-nitrobenzamide,benzhydroxamic acid, 2',5'-dichloroacetanilide, 2-cyanobenzamide,acetylacetanilide, 2'-methylacetanilide, 2,6-dichlorobenzamide,2'-chloroacetylacetanilide, 2'-methylacetylacetanilide, phenylacetamide,pyrazine-2-carboxamide, N-methyl-2-methylbenzamide, N-methylbenzamide,3,4,5-trimethoxybenzamide, 3-chloroacetanilide,4'-chloroacetylacetanilide, 4-nitrobenzamide, 2-cyanoacetanilide,2-chlorobenzamide, 2-nitrobenzamide, 3'-hydroxyacetanilide,3'-methylacetanilide, 3-chlorobenzamide, 4'-hydroxyacetanilide,2'-hydroxyacetanilide, 2-pyrrolidone, 1,2-benzisothiazol-3(2H)-one andthe like.

Method (g):

When the present compound is an acid amide compound represented by theformula (XVIII), ##STR45## wherein R¹, R³ and n represent the samemeanings as above, it can be produced, for example, by reacting acompound represented by the formula (XIX), ##STR46## wherein R¹, R³ andn represent the same meanings as above, with not less than theequivalent of phosphorus pentasulfide at 25° to 150° C. for 1 to 24hours in the presence or absence of a solvent.

The solvent used in the foregoing methods (c) to (g) includes forexample aliphatic hydrocarbons such as hexane, heptane, ligroin,petroleum ether, etc., aromatic hydrocarbons such as benzene, toluene,xylene, etc., halogenated hydrocarbons such as chloroform, carbontetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, etc.,ethers such as diethyl ether, diisopropyl ether, dioxane,tetrahydrofuran, diethylene glycol dimethyl ether, etc., ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone,cyclohexanone, etc., esters such as ethyl formate, ethyl acetate, butylacetate, diethyl carbonate, etc., nitro compounds such as nitroethane,nitrobenzene, etc., nitriles such as acetonitrile, isobutyronitrile,etc., tertiary amines such as pyridine, triethylamine,N,N-diethylaniline, (1.00 g, 10 mmoles), 2-cycloheptenylamine (1.11 g,10 mmoles) was added dropwise at 0° to 5° C. After stirring at 61° C.for 5 hours, the reaction mixture was cooled to obtain a crystal. Thecrystal was recrystallized from an ethyl acetate/hexane mixture toobtain 1.67 g of N-(2-cycloheptenyl)-1,4-butanedicarboxylic acidmonoamide [Compound (52)].

m.p. 132°-133° C.

Production example 6

To a dichloromethane solution (13 ml) containing salicylic acid (1.38 g,10 mmoles), dicyclohexylcarbodiimide (2.06 g, 10 mmoles) was slowlyadded at 0° C. After this mixture was stirred for 15 minutes, and2-cyclohexenylamine (0.97 g, 10 mmoles) was added dropwise. The mixturewas then heated to room temperature and stirred for 5 hours. The formedcrystal was filtered off, the floating solid was removed by filtrationand 13 ml of cold water was added to the filtrate. The organic layer wasseparated and washed with 3M hydrochloric acid, a saturated aqueoussodium hydrogencarbonate solution and a saturated aqueous sodiumchloride solution in this order. After drying the organic layer overmagnesium sulfate, the solvent was removed and the residual oil waspurified by column chromatography on silica gel [ethylacetate:hexane=3:1 (v/v)] to obtain 1.78 g ofN-(2-cyclohexenyl)salicylic acid amide [Compound (53)].

n_(D) ²².4 1.5781

Production example 7

To a suspension (10 ml) of sodium hydride (0.24 g, 10 mmoles) indimethylformamide was added dropwise at 0° C. a dimethylformamidesolution (1 ml) of N-methylbenzamide (1.35 g, 10 mmoles). Aftercompletion of the addition, the temperature was raised to roomtemperature, and after stirring for 15 minutes, 3-bromocycloheptene(1.75 g, 10 mmoles) was added dropwise. The resulting mixture wasstirred at room temperature for 24 hours, poured into water (20 ml) andextracted with ether. The oily product obtained by concentration waspurified by chromatography on silica gel to obtain 0.92 g ofN-methyl-N-(2-cycloheptenyl)benzamide [Compound (54)].

n_(D) ²⁶.1 1.5467

Production example 8

To a suspension (10 ml) of sodium hydride (0.24 g, 10 mmoles) in DMF wasadded N-(2-cycloheptenyl)acetamide (1.53 g, 10 mmoles) in DMF (1 ml) at0° C. After completion of the addition, the temperature of the mixturewas raised to room temperature, and after stirring for 15 minutes,methyl iodide (2.84 g, 20 mmoles) was added dropwise. The resultingmixture was stirred at room temperature for 24 hours, poured into water(20 ml) and extracted with ether. The oily product obtained byconcentration was purified by chromatography on silica gel to obtain0.84 g of N-methyl-N-(2-cycloheptenyl)acetamide [Compound (55)].

n_(D) ²⁴.5 1.4968

Production example 9

A mixture of N-(2-cyclohexenyl)-4-tert-butylbenzamide (3.78 g, 14.7mmoles), phosphorus pentasulfide (1.65 g) and pyridine (17.6 ml) washeated under reflux for 3 hours. Thereafter, the reaction mixture wascooled, poured into water and extracted with ether. The organic layerwas dried over anhydrous magnesium sulfate and concentrated. The oilyproduct obtained was purified by column chromatography on silica gel toobtain 0.71 g of the objective compound [Compound (205)].

m.p. 88°-91° C.

Some of the present compounds which can be produced by these methods areshown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Present compounds represented by the formula,                                  ##STR47##                                                                    Compound                                                                      No.   R.sup.1     R.sup.3           n X   Physical constant                   __________________________________________________________________________     (51) H           CH.sub.2 CH.sub.3 3 O   m.p. 84° C.                   (52) H           CH.sub.2 CH.sub.2 COOH                                                                          3 O   m.p. 132-133° C.              (53) H                                                                                          ##STR48##        2 O   n.sub.D.sup.22.4 1.5781              (54) CH.sub.3                                                                                   ##STR49##        3 O   n.sub.D.sup.26.1 1.5467              (55) CH.sub.3    CH.sub.3          3 O   n.sub.D.sup.24.5 1.4968              (56) H           CClCClCOOH        3 O   m.p. 139-140° C.(dec.)        (57) H           CCl.sub.3         3 O   m.p. 104-105° C.              (58) H           CCl.sub.3         3 NH  m.p. 85-87° C.                (59) H                                                                                          ##STR50##        3 O   m.p. 63-64° C.                (60) H           CH.sub.2 Cl       3 O   m.p. 92° C.                   (61) H                                                                                          ##STR51##        3 O   m.p. 120° C.                  (62) H                                                                                          ##STR52##        3 O   m.p. 92° C.                   (63) H                                                                                          ##STR53##        3 O   m.p. 113-114° C.              (64) H                                                                                          ##STR54##        3 O   m.p. 121° C.                  (65) H                                                                                          ##STR55##        3 O   m.p. 116° C.                  (66) H                                                                                          ##STR56##        3 O   m.p. 94° C.                   (67) H                                                                                          ##STR57##        3 O   m.p. 161° C.                  (68) H           CHCH.sub.2        3 O   m.p. 72-74° C.                (69) H           CH.sub.2 OCH.sub.3                                                                              3 O   m.p. 46-47° C.                (70) H                                                                                          ##STR58##        3 O   m.p. 147-148° C.              (71) H                                                                                          ##STR59##        3 O   m.p. 170° C.                  (72) H                                                                                          ##STR60##        3 O   m.p. 154-156° C.              (73) H                                                                                          ##STR61##        3 O   m.p. 89-91° C.                (74) H           CH.sub.2 CH.sub.2 COOCH.sub.3                                                                   3 O   m.p. 65-67° C.                (75) H                                                                                          ##STR62##        3 O   m.p. 120-121° C.              (76) H           CHCHCOOH          3 O   m.p. 114-115° C.              (77) H                                                                                          ##STR63##        3 O   m.p. 97-98° C.                (78) H                                                                                          ##STR64##        3 O   n.sub.D.sup.23.9 1.5910              (79) H           H                 3 O   n.sub.D.sup.22.5 1.5050              (80) H                                                                                          ##STR65##        3 O   m.p. 91° C.                   (81) H                                                                                          ##STR66##        3 O   m.p. 120-121° C.              (82) H                                                                                          ##STR67##        3 O   m.p. 132-134° C.              (83) H           C(CH.sub.2)CH.sub.2                                                                             3 O   n.sub.D.sup.25.5 1.4991                               COO(CH.sub.2).sub.2 CH.sub.3                                 (84) H                                                                                          ##STR68##        3 O   m.p. 117° C.                  (85) H                                                                                          ##STR69##        3 O   m.p. 117-118° C.              (86) H                                                                                          ##STR70##        3 O   m.p. 142° C.                  (87) H                                                                                          ##STR71##        3 O   m.p. 145-147° C.              (88) H                                                                                          ##STR72##        3 O   m.p. 145-147° C.              (89) H                                                                                          ##STR73##        3 O   m.p. 137-138° C.              (90) H                                                                                          ##STR74##        3 O   m.p. 174° C.                  (91) H           CH.sub.2 Br       3 O   m.p. 173-174° C.              (92) H           CH.sub.2 CH.sub.2 CH.sub.2                                                                      3 O   m.p. 76° C.                   (93) H                                                                                          ##STR75##        3 O   m.p. 168-169° C.              (94) H           C(CH.sub.3).sub.3 3 O   m.p. 119-120° C.              (95) H           CH.sub.2 CH.sub.2 Cl                                                                            3 O   m.p. 76-77° C                 (96) H           CH(CH.sub.3).sub.2                                                                              3 O   m.p. 138° C.                  (97) H                                                                                          ##STR76##        3 O   m.p. 150° C.                  (98) H           CH.sub.2 C(CH.sub.3).sub.3                                                                      3 O   m.p. 132-133° C.              (99) H           CH.sub.2 Oiso-Bu  3 O   n.sub.D.sup.24.5 1.4805             (100) H           CH.sub.2 CH(CH.sub.3).sub.2                                                                     3 O   m.p. 117° C.                 (101) H                                                                                          ##STR77##        3 O   m.p. 120-122° C.             (102) H                                                                                          ##STR78##        3 O   m.p. 156-158° C.             (103) H                                                                                          ##STR79##        3 O   m.p. 181-182° C.             (104) H                                                                                          ##STR80##        3 O   m.p. 133-135° C.             (105) H                                                                                          ##STR81##        3 O   m.p. 181-182° C.             (106) H           CHCHOC.sub.2 H.sub.5                                                                            3 O   m.p. 110-112° C.             (107) CH.sub.2 CN CH.sub.3          3 O   n.sub.D.sup.23.2 1.5040             (108) CH.sub.2 COOCH.sub.3                                                                      CH.sub.3          3 O   n.sub.D.sup.24.2 1.4817             (109) H                                                                                          ##STR82##        3 O   n.sub.D.sup.23.1 1.5770             (110) H                                                                                          ##STR83##        3 O   n.sub.D.sup.21.0 1.4950             (111) H                                                                                          ##STR84##        3 O   m.p. 113° C.                 (112) H                                                                                          ##STR85##        3 O   m.p. 143° C.                 (113) H                                                                                          ##STR86##        3 O   m.p. 92° C.                  (114) H                                                                                          ##STR87##        3 O   m.p. 176° C.                 (115) H                                                                                          ##STR88##        3 O   m.p. 126° C.                 (116) H                                                                                          ##STR89##        3 O   m.p. 93° C.                  (117) CH.sub.2 CHCH.sub.2                                                                       CH.sub.3          3 O   n.sub.D.sup.23.7 1.5021             (118)                                                                                ##STR90##  CH.sub.3          3 O   n.sub.D.sup.23.5 1.5076             (119) CH.sub.2 CCH                                                                              CH.sub.3          3 O   n.sub.D.sup.28.5 1.5131             (120)                                                                                ##STR91##  CH.sub.3          3 O   n.sub.D.sup.20.7 1.5162             (121)                                                                                ##STR92##  CH.sub.3          3 O   n.sub.D.sup.25.3 1.5329             (122) CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                      CH.sub.3          3 O   n.sub.D.sup.23.3 1.4850             (123) H           CH.sub.3          3 O   J.Org.Chem. 46,                                                               4727 (1981)                         (124) H                                                                                          ##STR93##        3 O   m.p. 118° C.                 (125)                                                                                ##STR94##  CH.sub.2 Cl       3 O   n.sub.D.sup.24.8 1.5373             (126) H           CH.sub.2 CN       3 O   m.p. 131° C.                 (127) CH(CH.sub.3).sub.2                                                                        CH.sub.2 Cl       3 O   n.sub.D.sup.23.3 1.5044             (128)                                                                                ##STR95##                                                                                 ##STR96##        3 O   m.p. 147° C.                 (129) H                                                                                          ##STR97##        3 O   m.p. 153° C.                 (130) CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                      CH.sub.2 Cl       3 O   n.sub.D.sup.26.6 1.5000             (131) H                                                                                          ##STR98##        3 O   m.p. 123° C.                 (132)                                                                                ##STR99##  CHCl.sub.2        3 O   n.sub.D.sup.26.1 1.5467             (133) H           (CH.sub.2).sub. 4 Cl                                                                            3 O   m.p. 71° C.                  (134) (CH.sub.2).sub.5 Cl                                                                       CH.sub.3          3 O   n.sub.D.sup.22.5 1.4966             (135) CH.sub.2 CH.sub.2 CH.sub.2    3 O   n.sub.D.sup.24.3 1.5175             (136) CHCH.sub.3 COOCH.sub.3                                                                    CH.sub.2 OCH.sub.3                                                                              3 O   n.sub.D.sup.23.7 1.4886             (137) H                                                                                          ##STR100##       3 O   m.p. 126° C.                 (138) H           CH.sub.2 CH.sub.3 2 O   m.p. 80-82° C.               (139) H           CH.sub.2 CH.sub.2 COOH                                                                          2 O   m.p. 143-144° C.             (140) H           CHCHCOOH          2 O   m.p. 113-114° C.             (141) H                                                                                          ##STR101##       2 O   m.p. 91-93° C.               (142) H                                                                                          ##STR102##       2 O   m.p. 108-111° C.             (143) H                                                                                          ##STR103##       2 O   m.p. 128-130° C.             (144) H                                                                                          ##STR104##       2 O   m.p. 113-114° C.             (145) H                                                                                          ##STR105##       2 O   m.p. 162-164° C.             (146) H                                                                                          ##STR106##       2 O   m.p. 118-120° C.             (147) H                                                                                          ##STR107##       2 O   m.p. 90-90° C.               (148) H                                                                                          ##STR108##       2 O   m.p. 133-135° C.             (149) H                                                                                          ##STR109##       2 O   n.sub. D.sup.25.3 1.5568            (150) H                                                                                          ##STR110##       2 O   m.p. 101-103° C.             (151) H                                                                                          ##STR111##       2 O   m.p. 120-122° C.             (152) H                                                                                          ##STR112##       2 O   m.p. 160-162° C.             (153) H                                                                                          ##STR113##       2 O   m.p. 143-145° C.             (154) CH.sub.2 CH.sub.3                                                                         CH.sub.3          2 O   n.sub.D.sup.20.1 1.4840             (155) H                                                                                          ##STR114##       2 O   m.p. 86-87° C.               (156) H                                                                                          ##STR115##       2 O   m.p. 116-118° C.             (157) H                                                                                          ##STR116##       2 O   m.p. 122-123° C.             (158) H                                                                                          ##STR117##       2 O   m.p. 115-116° C.             (159) H           CH(CH.sub.3).sub.2                                                                              2 O   m.p. 107-108° C.             (160) H           (CH.sub.2).sub.12 CH.sub.3                                                                      2 O   m.p. 82-83° C.               (161) H                                                                                          ##STR118##       2 O   m.p. 165-166° C.             (162) H           CH.sub.2 C(CH.sub.3).sub.3                                                                      2 O   m.p. 118-121° C.             (163) H                                                                                          ##STR119##       2 O   m.p. 107-108° C.             (164) H                                                                                          ##STR120##       2 O   m.p. 125-126° C.             (165) H           CHCHCH.sub.3      2 O   m.p. 86-89° C.               (166) H           CH.sub.2 C(CH.sub.2)COOH                                                                        2 O   m.p. 140-141° C.             (167) H                                                                                          ##STR121##       2 O   m.p. 116-119° C.             (168) H           CHCl.sub.2        2 O   m.p. 128-129° C.             (169) H                                                                                          ##STR122##       2 O   m.p. 94-95° C.               (170) H                                                                                          ##STR123##       2 O   m.p. 115-120°  C.            (171) CH.sub.2 CN CH.sub.2 Cl       2 O   n.sub.D.sup.17.3 1.4855             (172)                                                                                ##STR124## CH.sub.2 Cl       2 O   n.sub.D.sup.17.6 1.5650             (173) CH.sub.2 COOCH.sub.3                                                                      CH.sub.2 Cl       2 O   n.sub.D.sup.17.5 1.5070             (174) H                                                                                          ##STR125##       1 O   m.p. 116-117° C.             (175) H                                                                                          ##STR126##       4 O   m.p. 157-158° C.             (176) H                                                                                          ##STR127##       2 O   m.p. 134-135° C.             (177) H                                                                                          ##STR128##       2 O   m.p. 90-91° C.               (178) H                                                                                          ##STR129##       2 O   m.p. 141-142° C.             (179) H                                                                                          ##STR130##       2 O   m.p. 150-151° C.             (180) H                                                                                          ##STR131##       2 O   m.p. 136-138° C.             (181) H           CH.sub.2 OCH.sub.3                                                                              2 O   n.sub.D.sup.25.5 1.4866             (182) H                                                                                          ##STR132##       2 O   m.p. 62-63° C.               (183) H                                                                                          ##STR133##       2 O   n.sub.D.sup.20.5 1.4920             (184) H                                                                                          ##STR134##       2 O   m.p. 109-112° C.             (185) H                                                                                          ##STR135##       2 O   m.p. 110-111° C.             (186) H           CH.sub.3          2 O   J.Am.Chem.Soc., 94,                                                           7892 (1972)                         (187) H           CH.sub.2 Cl       2 O   Can.J.Chem. 55,                                                               700 (1977)                          (188) H           C(CH.sub.3).sub.3 2 O   J.Am.Chem.Soc.89,                                                             6303 (1967)                         (189) H                                                                                          ##STR136##       2 O   J.Am.Chem.Soc.80, 4312 (1958)       (190) H           CCl.sub.3         2 O   J.Am.Chem.Soc.98,                                                             2901 (1976)                         (191) H           CHCHCl            2 O   m.p. 87-88° C.               (192) H           H                 2 O   n.sub.D.sup.20.0 1.5050             (193) H           CH.sub.2 CN       2 O   m.p. 110-115° C.             (194) H                                                                                          ##STR137##       2 O   m.p. 67-68° C.               (195) H                                                                                          ##STR138##       2 O   m.p. 153-156° C.             (196) H           CCl.sub.3         2 NH  Ger.Offen.2,601,137                 (197) H           CF.sub.2 CF.sub.3 2 O   m.p. 72-73° C.               (198) H                                                                                          ##STR139##       2 O   m.p. 120-122° C.             (199) H                                                                                          ##STR140##       2 O   m.p. 170-172° C.             (200) H                                                                                          ##STR141##       2 O   m.p. 85-86° C.               (201) H                                                                                          ##STR142##       2 O   m.p. 70-75° C.               (202) H                                                                                          ##STR143##       2 O   m.p. 138- 139° C.            (203) H           CH.sub.3          2 S   m.p. 57-59° C.               (204) H                                                                                          ##STR144##       2 O   m.p. 129-130° C.             (205) H                                                                                          ##STR145##       2 S   m.p. 88-91° C.               (206) H                                                                                          ##STR146##       2 O   Resinous product                    (207) H           CClCClCOOH        2 O   m.p. 106-109° C.             (208) CH(CH.sub.3)COOCH.sub.3                                                                   CH.sub.2 Cl       2 O   n.sub.D.sup.24.0 1.5090             (209) H                                                                                          ##STR147##       2 O   m.p. 108-110° C.             (210) H                                                                                          ##STR148##       2 O   m.p. 152° C.                 (211) H                                                                                          ##STR149##       2 O   m.p. 110-112° C.             (212) CH.sub.2 CH.sub.2 CH.sub.2     2                                                                              O   n.sub.D.sup.26.5 1.5101             (213)                                                                                ##STR150##                   2 O   n.sub.D.sup.24.8                    __________________________________________________________________________                                              1.6314                          

Method (h):

When the present compound is an acid imide compound represented by theformula (XX), ##STR151## wherein X, Y, Z and n represent the samemeanings as above, provided that a case wherein when n is 2 or 3 and Xand Y are an oxygen atom, Z is an o-phenylene group, is excluded, it canbe produced by reacting cycloalkenylamine represented by the formula(XXI), ##STR152## wherein n represents the same meaning as above, with0.9 to 1.0 equivalent of a compound represented by the formula (XXII),##STR153## wherein X, Y and Z represent the same meanings as above, orits anhydride, i.e. a compound represented by the formula (XXIII),##STR154## wherein X, Y and Z represent the same meanings as above, withor without a solvent at 80° to 180° C., preferably 130° to 160° C. for 1to 30 hours in the presence or absence of a catalyst.

As the compound represented by the formula (XXII), there are given forexample succinic acid, 1,2-cyclohexanedicarboxylic acid, maleic acid,citraconic acid, isopropylidenesuccinic acid, 3,4,5,6-tetrahydrophthalicacid, mellitic acid, 4-carboxyphthalic acid, dichloromaleic acid,phenylmaleic acid, tetrachlorophthalic acid, tetrabromophthalic acid,3-nitrophthalic acid, 1,2-pyridinedicarboxylic acid,3,4-furandicarboxylic acid, glutaric acid, 2,2-dimethylglutaric acid,3,4-pyrazinedicarboxylic acid, 3,3-dimethylglutaric acid, dimethylmaleicacid, naphthalic acid, 1,2-cyclobutanedicarboxylic acid,monochloromaleic acid, monobromomaleic acid, dibromomaleic acid,monofluoromaleic acid, difluoromaleic acid, malic acid, thiomalic acid,methoxysuccinic acid, 2-methyl-2-phenylsuccinic acid, acetoxysuccinicacid, acetylthiosuccinic acid, tetrafluorophthalic acid,5-norbornane-2,3-dicarboxylic acid,1,2-dimethyl-1,2-cyclopropanedicarboxylic acid, itaconic acid, camphanicacid, diphenic acid, diphenylcarbamoyloxysuccinic acid,phenylcarbamoyloxysuccinic acid,cis,cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid,bicyclo[2,2,2]octa-5-ene-2,3-dicarboxylic acid and the like. As thecompound represented by the formula (XXIII), there are given theanhydrides of the compounds represented by the foregoing formula (XXII).

Method (i):

When the present compound is an acid imide compound represented by theforegoing formula (XX) (provided that a case wherein when n is 1, 2 or 3and X and Y are an oxygen atom, Z is an o-phenylene group, is excluded),it can be produced by reacting a compound represented by the foregoingformula (VII) with 1.0 to 1.1 equivalent of a compound represented bythe formula (XXIV), ##STR155## wherein X, Y and Z represent the samemeanings as above, with or without a solvent at 0° to 200° C.,preferably 20° to 160° C. for 1 to 24 hours in the presence of 1.0 to1.1 equivalent of an acid-binding agent.

As the compound represented by the formula (XXIV), there are given forexample acid imides corresponding to the compounds represented by theforegoing formula (XXIII) and the compounds described below:

5,5-Dimethyl-2-thioxo-4-oxazolidinone

5,5-Dimethyl-4-thioxo-2-oxazolidinone

5,5-Dimethyl-2,4-thiazolidinedione

2-Thioxo-4-imidazolidinone

2,4-Imidazolidinedione

5,5-Dimethyl-2,4-oxazolidinedione

5,5-Dimethyl-2-thioxo-4-imidazolidinone

5,5-Dimethyl-2,4-imidazolidinedione

5,5-Dimethyl-2-thioxo-4-thiazolidinone

5-Imino-2-pyrrolidinone

Method (j):

When the present compound is an acid imide compound represented by theformula (XXV), ##STR156## wherein X, Z and n represent the same meaningsas above, it can be produced by reacting an acid imide compoundrepresented by the formula (XXVI), ##STR157## wherein X, Z and nrepresent the same meanings as above, with 1 or 2 equivalents ofphosphorus pentasulfide at 25° C. to 150° C. for 1 to 24 hours in thepresence or absence of a solvent.

The acid imide compound represented by the formula (XXVI) is obtained bythe foregoing method.

The solvent used in the methods (h) to (j) includes for examplealiphatic hydrocarbons such as hexane, heptane, ligroin, petroleumether, etc., aromatic hydrocarbons such as benzene, toluene, xylene,etc., halogenated hydrocarbons such as chloroform, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether, etc., fatty acids such as formic acid, aceticacid, oleic acid, etc., alcohols such as methanol, ethanol, isopropanol,tert-butanol, octanol, cyclohexanol, methyl cellosolve, diethyleneglycol, glycerin, etc., nitro compounds such as nitroethane,nitrobenzene, etc., nitriles such as acetonitrile, isobutyronitrile,etc., tertiary amines such as pyridine, triethylamine,N,N-diethylaniline, tributylamine, N-methylmorpholine, etc., sulfurcompounds such as dimethyl sulfoxide, sulfolane, etc., water andmixtures thereof.

Also, the acid-binding agent includes for example organic bases such aspyridine, triethylamine, N,N-diethylaniline, etc. and inorganic basessuch as sodium carbonate, potassium carbonate, sodium hydrogencarbonate,potassium hydroxide, sodium hydroxide, sodium hydride, etc.

After completion of the reaction, the reaction solution is after-treatedas usual, for example an organic solvent is added to the solution whichis then washed with an alkali and water to obtain the objectivecompound. If necessary, the compound obtained is purified bychromatography, distillation, recrystallization and the like.

Next, examples of production of the present compound by the methods (h)to (j) will be shown.

Production example 10

A mixture of 2-cycloheptenylamine (1.01 g), succinic anhydride (1.0 g)and acetic acid (10 ml) was heated under reflux for 24 hours. Aftercooling, ether (20 ml) was added to the reaction mixture which was thenwashed with a saturated aqueous sodium hydrogencarbonate solution, waterand a saturated aqueous sodium chloride solution in this order. Theorganic layer was dried over anhydrous magnesium sulfate andconcentrated. The oily product thus obtained was purified by columnchromatography on silica gel to obtain 1.07 g ofN-(2-cycloheptenyl)succinimide [Compound (214)].

n_(D) ²⁴.3 1.4872

Production example 11

A mixture of N-2-cycloheptenyl-3,4,5,6-tetrahydrophthalimide (3.75 g),phosphorus pentasulfide (3,40 g) and toluene (10 ml) was heated underreflux for 5 hours. The reaction mixture was cooled, poured into waterand extracted with ether. The organic layer was dried over anhydrousmagnesium sulfate and concentrated. The oil obtained was purified bycolumn chromatography on silica gel to obtain 1.51 g of the objectivecompound [Compound (215)].

n_(D) ²².5 1.6604

Production example 12

A mixture of 2-cycloheptenylamine (1.11 g),1,2-dimethyl-1,2-cyclopropanedicarboxylic acid (1.58 g) and toluene (30ml) was heated, and formed water was removed azeotropically. Thereafter,the mixture was concentrated, and the oily product obtained was purifiedby chromatography on silica gel to obtain 1.26 g ofN-(2-cycloheptenyl)-1,2-dimethyl-1,2-cyclopropanedicarboxyimide[Compound (216)].

m.p. 57°-59° C.

Production example 13

A mixture of 2-cycloheptenylamine (1.01 g), dichloromaleic anhydride(1.67 g) and acetic acid (10 ml) was heated under reflux for 3 hours.After cooling, ether (20 ml) was added to the reaction mixture which wasthen washed with a saturated aqueous sodium hydrogencarbonate solution,water and a saturated aqueous sodium chloride solution in this order.The organic layer was dried over anhydrous magnesium sulfate andconcentrated. The deposited crystal was purified by recrystallizationfrom hexane to obtain 1.67 g of N-(2-cycloheptenyl)dichloromaleinimide[Compound (217)].

m.p. 90°-91° C.

Production example 14

3-Bromocycloheptene (1.75 g) was added dropwise at room temperature to aDMF suspension (10 ml) of sodium succinimide prepared from succinimide(0.99 g) and 60% sodium hydride (0.40 g). This mixture was stirred atroom temperature for 24 hours, poured into water (10 ml) and extractedwith ether. The oily product obtained by concentration was purified bychromatography on silica gel to obtain 0.09 g ofN-(2-cycloheptenyl)succinimide [Compound (214)].

n_(D) ²⁴.2 1.4875

Some of the present compounds similarly obtained are shown collectivelyin Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Present compounds represented by the formula,                                  ##STR158##                                                                   Compound                                                                      No.   X Y Z                   n Physical constant                             __________________________________________________________________________    (214) O O CH.sub.2 CH.sub.2   3 n.sub.D.sup.24.3 1.4872                       (215) S S                                                                                ##STR159##         3 n.sub.D.sup.22.5 1.6004                       (216) O O                                                                                ##STR160##         3 m.p. 57-59° C.                         (217) O O CClCCl              3 m.p. 90-91° C.                         (218) O O SC(CH.sub.3).sub.2  3 m.p. 86-88° C.                         (219) O O CBrCBr              3 m.p. 134-135° C.                       (220) O O CClCH               3 m.p. 100° C.                           (221) O O CBrCH               3 m.p. 114-116° C.                       (222) O O CHCH                3 n.sub.D.sup.25.9 1.5732                       (223) O O C(CH.sub.3)CH       3 n.sub.D.sup.22.6 1.5748                       (224) O O C(CH.sub.2)CH.sub.2 3 n.sub.D.sup.22.6 1.5862                       (225) O O                                                                                ##STR161##         3 n.sub.D.sup.19.3 1.5892                       (226) O O                                                                                ##STR162##         3 m.p. 175-177° C.                       (227) O O                                                                                ##STR163##         3 m.p. 156° C.                           (228) O O                                                                                ##STR164##         3 m.p. 81-83° C.                         (229) O O                                                                                ##STR165##         3 m.p. 84-86° C.                         (230) O O CH.sub.2CH(OH)      3 m.p. 121-123° C.                       (231) O O CH.sub.2 CH(SH)     3 m.p. 64-67° C.                         (232) O O CH.sub.2 CH(OCH.sub.3)                                                                            3 n.sub.D.sup.33.0 1.5621                       (233) O O                                                                                ##STR166##         3 m.p. 86-88° C.                         (234) O O                                                                                ##STR167##         3 m.p. 93-95° C.                         (235) O O                                                                                ##STR168##         3 n.sub.D.sup.21.7 1.5741                       (236) O O                                                                                ##STR169##         3 n.sub.D.sup.25.3 1.5329                       (237) O O                                                                                ##STR170##         3 n.sub.D.sup.22.5 1.5505                       (238) S O NHCH.sub.2          3 m.p. 148° C.                           (239) O O                                                                                ##STR171##         3 m.p. 102° C.                           (240) O O C(CH.sub.3)C(CH.sub.3)                                                                            3 n.sub.D.sup.27.4 1.5689                       (241) O O                                                                                ##STR172##         3 m.p. 53° C.                            (242) S O SCH.sub.2           3 n.sub.D.sup.22.0 1.5535                       (243) O O                                                                                ##STR173##         3 m.p. 173-174° C.                       (244) O O                                                                                ##STR174##         3 Eur. J. Med. Chem. 13, 81 (1978)              (245) O O CH.sub.2 CH.sub.2   2 n.sub.D.sup.28.2 1.5192                       (246) O O CHCH                2 n.sub.D.sup.23.6 1.5211                       (247) O O CClCCl              2 m.p. 89° C.                            (248) O O                                                                                ##STR175##         2 Chem. & Ind. 414, (1958)                      (249) O O                                                                                ##STR176##         2 m.p. 46-48° C.                         (250) O O                                                                                ##STR177##         1 m.p. 41-44° C.                         (251) O O C(CH.sub.3)CH       4 n.sub.D.sup.20.4 1.5227                       (252) O O C(CH.sub.2)CH.sub.2 4 n.sub.D.sup.20.4 1.5331                       (253) O S                                                                                ##STR178##         2 m.p. 45-48° C.                         (254) O O                                                                                ##STR179##         2 n.sub.D.sup.18.2 1.5361                       (255) O O                                                                                ##STR180##         2 m.p. 100-101° C.                       (256) O O                                                                                ##STR181##         2 m.p. 76° C.                            (257) O O                                                                                ##STR182##         2 m.p. 67° C.                            (258) O O                                                                                ##STR183##         2 m.p. 140° C.                           (259) O O CClCCl              4 m.p. 63-64° C.                         (260) O O                                                                                ##STR184##         2 n.sub.D.sup.25.0 1.5079                       (261) O O OC(CH.sub.3).sub.2  2 m.p. 69-71° C.                         (262) O S NHCH.sub.2          2 m.p. 106-108° C.                       (263) O O CHCCl               2 m.p. 78° C.                            (264) O O CHCBr               2 m.p. 90-91° C.                         (265) O O C(CH.sub.3)CH       2 m.p. 65-66°  C.                        (266) O O CClCCl              1 m.p. 52° C.                            (267) O O NHCH.sub.2          2 m.p. 91° C.                            (268) O O C(CH.sub.3)C(CH.sub.3)                                                                            2 n.sub.D.sup.25.2 1.5178                       (269) O O CH.sub.2 CH(SCOOCH.sub.3)                                                                         2 n.sub.D.sup.29.5 1.5344                       (270) O O                                                                                ##STR185##         2 n.sub.D.sup.29.5 1.5220                       (271) O O                                                                                ##STR186##         2 m.p. 97° C.                            (272) O O CH(OH)CH.sub.2      2 m.p. 108-110° C.                       (273) O O CH(OCOCH.sub.3)CH.sub.2                                                                           2 m.p. 96° C.                            (274) O O CH(OCH.sub.3)CH.sub.2                                                                             2 n.sub.D.sup.30.7 1.5110                       (275) O O CH(SH)CH.sub.2      2 n.sub.D.sup.29.7 1.5490                       (276) O O                                                                                ##STR187##         2 m.p. 165-168° C.                       (277) O O CBrCBr              2 m.p. 81° C.                            __________________________________________________________________________

Method (k):

When the present compound is an imine compound represented by theformula (XXVII), ##STR188## wherein R⁴, R⁵ and n represent the samemeanings as above, provided that the following cases are excluded: whenn is 1, R⁴ is a butyl group and R⁵ is a pentyl group, or R⁴ and R⁵,taken together, form a 2,4,4-trimethyl-1-pentenylene group; and when nis 2, R⁴ and R⁵, taken together, form a pentenylene group, it can beproduced by reacting cycloalkenylamine represented by the foregoingformula (XXI) with 0.95 to 1.0 equivalent of a carbonyl compoundrepresented by the formula (XXVIII), ##STR189## wherein R⁴ and R⁵represent the same meanings as above, at 0° to 150° C. for 1 to 24 hourswith or without a solvent.

As the carbonyl compound represented by the above formula (XXVIII),there are given for example formaldehyde, acetaldehyde, propionaldehyde,glyoxylic acid, methoxyacetaldehyde, butylaldehyde, isobutylaldehyde,n-valeraldehyde, isovaleraldehyde, 2-methylbutylaldehyde, hexanal,heptanal, octanal, decanal, β-phenylpropionaldehyde, dodecanal,5-norbornane-2-carboaldehyde, cyclohexanecarboaldehyde,cyclooctanecarboaldehyde, 2-ethylbutanal, phenylacetaldehyde,chloroacetaldehyde, chloral, cinnamaldehyde, α-methylcinnamaldehyde,α-bromocinnamaldehyde, α-chlorocinnamaldehyde, acrolein, acrolein dimer,metacrolein, crotonaldehyde, trans-2-hexenylaldehyde, 2-ethyl-2-butenal,2-ethylhexanal, citral, citronellal, phenylpropargylaldehyde,DL-glyceraldehyde, aldol, glyoxal, terephthalaldehyde, benzaldehyde,o-fluorobenzaldehyde, α,α,α-trifluoro-m-tolualdehyde,pentafluorobenzaldehyde, m-bromobenzaldehyde,3,5-diiodo-4-hydroxybenzaldehyde, o-chlorobenzaldehyde,3,5-dichlorobenzaldehyde, 3,5-dichlorosalicylaldehyde,2-chloro-6-fluorobenzaldehyde, 2,3,6trichlorobenzaldehyde,2,5-dichloro-4-nitrobenzaldehyde, 2,4,5-trichloro-3-nitrobenzaldehyde,salicylaldehyde, 5-bromosalicylaldehyde, vanillin,2-carboxybenzaldehyde, 5-chlorosalicylaldehyde,p-methylthiobenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde,3-ethoxy-4-hydroxybenzaldehyde, 5-nitrosalicylaldehyde,4-hydroxy-3,5-di-tert-butylbenzaldehyde, p-anisaldehyde,2,5-dimethoxybenzaldehyde, m-[m-(trifluoromethyl)phenoxy]benzaldehyde,5-bromo-o-anisaldehyde, 3-chloro-4-hydroxy-5-ethoxybenzaldehyde,4-hydroxy-5-bromo-m-anisaldehyde, o-ethoxybenzaldehyde,2,3-dimethyl-4-methoxybenazaldehyde,4-[β-(diethylamino)ethoxy]benzaldehyde, piperonal, 6-nitropiperonal,3-methyl-p-anisaldehyde, m-(p-chlorophenoxy)benzaldehyde,3-benzyloxybenzaldehyde, p-phenoxybenzaldehyde,3,4,5-trimethoxybenzaldehyde, methyl 4-formylbenzoate,o-nitrobenzaldehyde, p-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde,3-methoxy-2-nitrobenzaldehyde, 4-fluoro-2-nitrobenzaldehyde,5-hydroxy-2-nitrobenzaldehyde, p-cyanobenzaldehyde,2,4-dimethylbenzaldehyde, o-tolualdehyde, cuminaldehyde,α-naphthaldehyde, p-phenylbenzaldehyde, p-dimethylaminobenzaldehyde,5-formyl-2-furansulfonic acid, p-acetaminobenzaldehyde,5-methylfurfural, 2-thiophenecarboaldehyde, β-2-furylacrolein,nicotinaldehyde, furfural, 5-nitrofurfural,5-methyl-2-thiophenecarboaldehyde, N-methylpyrrole-2-carboaldehyde,chloroacetone, bromoacetone, hydroxyacetone, α,α'-dichloroacetone,hexachloroacetone, methyl ethyl ketone, methyl vinyl ketone, diacetyl,3-chloro-2-butanone, cyclobutanone, acetoin, methoxyacetone,perchloro-2-cyclobuten-1-one, 3-methyl-2-butanone, 2-pentanone,cyclopentanone, 3-penten-2-one, acetylacetone, pinacolone,bromopinacolone, 3-hexanone, mesityl oxide, 4-methyl-2-pentanone,acetonylacetone, cyclohexanone, 1,2-cyclohexanedione,1,4-cyclohexanedione, 2-cyclohexen-1-one, 3-methyl-2-cyclopenten-1-one,3-methylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, methyl1-methylcyclopropyl ketone, 2-methylcyclohexanone,2-methyl-1,3-cyclohexanedione, 5-methyl-2-hexanone, 2-heptanone,dimedone, 2-octanone, 2-methyl-2-hepten-6-one,3,5-dimethyl-2-cyclohexen-1-one, isophorone, phorone,2,6-dimethyl-4-heptanone, 4-tert-butylcyclohexanone, menthone,l-carvone, β-ionone, DL-camphor, 6-methoxy-1-tetralone, 6-undecanone,5-nonanone, quinone, di-tert-butyl-p-quinone,2,5-dichloro-p-benzoquinone, 2,3 -dichloro-1,4-naphthoquinone,2-hydroxy-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone,anthraquinone, phenanthrenequinone, 2,6-dihydroxyanthraquinone,acetophenone, o-hydroxyacetophenone, p-nitroacetophenone,m-chloroacetophenone, o-fluoroacetophenone, p-bromoacetophenone,2,4-dichloroacetophenone, 2,4-dihydroxyacetophenone,α,α-dichloroacetophenone, α-bromoacetophenone,2,3,4-trichloroacetophenone, α-chloroacetophenone,p-methoxyacetophenone, o-methylacetophenone,α,α,α-trifluoroacetophenone, p-chlorophenacyl bromide,α-methoxyacetophenone, propiophenone, p-chloropropiophenone,p-fluoropropiophenone, 2-hydroxy-5-methylacetophenone, phenoxyacetone,1-indanone, 1,3-indanedione, phenyl n-propyl ketone,α-bromoisobutyrophenone, phenyl propenyl ketone, o-hydroxybutyrophenone,benzoylacetone, 3,4-dimethylacetophenone, cyclopropyl phenyl ketone,benzalacetone, 4-methoxypropiophenone, 2,4,6-trimethylacetophenone,valerophenone, β-acetonaphthone, hexaphenone, 2-acetyl-1-tetralone,benzophenone, p-chlorobenzophenone, 2-chloro-5-nitrobenzophenone,4-hydroxybenzophenone, 2,4-dihydroxybenzophenone,5-chloro-2-hydroxybenzophenone, 9-fluorenone, benzoyl, benzil,deoxybenzoin, 4-acetylbiphenyl, p-phenyl-60-bromoacetophenone, acridone,4-methoxy-2-hydroxybenzophenone, anthrone, dibenzoylmethane,benzalacetophenone, 2-hydroxychalcone, tetrahydrothiopyran-4-one,bis-3,4-methylenedioxybenzil,2,2'-dihydroxy-4,4'-dimethoxylbenzophenone,2'-carboxy-2-hydroxy-4-methoxybenzophenone,2'-(o-chlorobenzoyl)-2,4'-dichloroacetanilide,4,4'-bis(dimethylamino)benzophenone, 5,7-dichloroisatin, 6-chloroisatin,isatin, 5-nitroisatin,3-(hexahydro-1H-azepin-1-yl)-3'-nitropropiophenone,s-triazolo[4,3,α]-pyrido-3(2H)-one, perinaphthenone, thioxanthen-9-one,xanthone, 2-acetylpyridine, 3-benzoylpyridine, di-2-pyridyl ketone,di-pyridylglyoxal, 3,5-diiodo-4-pyridone, 3-acetyl-2,4-dimethylpyrrole,pyrrole-2-carboaldehyde, 2,2,6,6-tetramethyl-4-piperidone,1-methyl-4-piperidone, methyl 4-oxo-3-piperidinecarboxylate and thelike.

The solvent used in this method (k) includes for example aliphatichydrocarbons such as hexane, heptane, ligroin, petroleum ether, etc.,aromatic hydrocarbons such as benzene, toluene, xylene, etc.,halogenated hydrocarbons such as chloroform, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether, etc., alcohols such as methanol, ethanol,isopropanol, tert-butanol, octanol, cyclohexanol, methyl cellosolve,diethylene glycol, glycerin, etc., esters such as ethyl formate, ethylacetate, butyl acetate, diethyl carbonate, etc., nitro compounds such asnitroethane, nitrobenzene, etc., nitriles such as acetonitrile,isobutyronitrile, etc., tertiary amines such as pyridine, triethylamine,N,N-diethylaniline, tributylamine, N-methylmorpholine, etc., acid amidessuch as formamide, N,N-dimethylformamide, acetamide, etc., sulfurcompounds such as dimethyl sulfoxide, sulfolane, etc., water andmixtures thereof.

The catalyst used includes for example benzenesulfonic acid,p-toluenesulfonic acid, phosphoryl chloride, boron trifluoride, titaniumtetrachloride and the like.

After completion of the reaction, the common after-treatment is carriedout and if necessary, the product obtained is purified bychromatography, distillation, recrystallization and the like.

Next, examples of production of the present compound by the method (k)will be shown.

Production Example 15

A mixture of 2-cycloheptenylamine (11.1 g, 0.1 mole), benzaldehyde (10.6g, 0.1 mole) and benzene (50 ml) was heated under reflux, and resultingwater was removed by azeotropic distillation. The mixture wasconcentrated to obtain 16.7 g of n-benzylidene-2-cycloheptenylamine[Compound (280)].

n_(D) ²².3 1.5631

Production example 16

A mixture of 2-cyclohexenylamine (9.7 g, 0.1 mole), cyclohexanone (9.8g, 0.1 mole), zinc chloride (0.16 g) and benzene (50 ml) was heatedunder reflux, and resulting water removed by azeotropic distillation.The mixture was concentrated and distilled to obtain 12.4 g ofN-cyclohexylidene-2-cyclohexenylamine [Compound (344)].

b.p. 91°-93° C./2 mmHg

Some of the present compounds which can be produced by this method areshown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________    Present compounds represented by the formula,                                  ##STR190##                                                                   Compound                                                                      No.   R.sup.4                                                                             R.sup.5             n Physical constant                           __________________________________________________________________________    (278) H                                                                                    ##STR191##         2 n.sub.D.sup.24.1 1.5135                     (279) H                                                                                    ##STR192##         3 n.sub.D.sup.23.7 1.5476                     (280) H                                                                                    ##STR193##         3 n.sub.D.sup.22.3 1.5631                     (281) H     CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.2CHC(CH.sub.3).sub.2                                         3 n.sub.D.sup.22.7 1.4876                     (282) H                                                                                    ##STR194##         3 n.sub.D.sup.25.3 1.5004                     (283) H     CH.sub.2 CH.sub.3   3 n.sub.D.sup.23.0 1.4823                     (284) H                                                                                    ##STR195##         3 n.sub.D.sup.23.5 1.5406                     (285) H                                                                                    ##STR196##         3 n.sub. D.sup.24.2 1.5855                    (286) H                                                                                    ##STR197##         3 n.sub.D.sup.24.2 1.5637                     (287) H                                                                                    ##STR198##         3 n.sub.D.sup.25.3 1.6192                     (288) H                                                                                    ##STR199##         3 n.sub.D.sup.24.2 1.6279                     (289) H     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                               3 n.sub.D.sup.24.3 1.4797                     (290) H     CH.sub.2 OCH.sub.3  3 n.sub.D.sup.24.0 1.4916                     (291) H     CH(CH.sub.3).sub.2  3 n.sub.D.sup.23.9 1.4785                     (292) H                                                                                    ##STR200##         3 n.sub.D.sup.23.5 1.5792                     (293) H                                                                                    ##STR201##         3 n.sub.D.sup.24.2 1.5869                     (294) H                                                                                    ##STR202##         3 n.sub.D.sup.24.2 1.5994                     (295) H                                                                                    ##STR203##         3 n.sub.D.sup.23.0 1.5919                     (296) H                                                                                    ##STR204##         3 m.p. 114-115° C.                     (297) H                                                                                    ##STR205##         3 n.sub.D.sup.21.5 1.5589                     (298) H                                                                                    ##STR206##         3 n.sub.D.sup.21.9 1.5532                     (299) H                                                                                    ##STR207##         3 n.sub.D.sup.22.2 1.5502                     (300) H                                                                                    ##STR208##         3 m.p. 42° C.                          (301) H                                                                                    ##STR209##         3 n.sub.D.sup.23.5 1.5725                     (302) H                                                                                    ##STR210##         3 n.sub.D.sup.24.1 1.5769                     (303) H                                                                                    ##STR211##         3 n.sub.D.sup.23.6 1.5488                     (304) CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                            3 b.p. 79-83° C./0.75 mmHg             (305) H                                                                                    ##STR212##         3 n.sub.D.sup.23.6 1.5116                     (306) H                                                                                    ##STR213##         3 n.sub.D.sup.23.9 1.5640                     (307) CH.sub.2 CH.sub.3                                                                    ##STR214##         3 b.p. 111-114° C./1.2 mmHg            (308) CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3)CH                                                       3 b.p. 103-106° C./0.8 mmHg            (309) H                                                                                    ##STR215##         2 n.sub.D.sup.27.0 1.5692                     (310) H                                                                                    ##STR216##         2 n.sub.D.sup.25.5 1.5672                     (311) H                                                                                    ##STR217##         2 n.sub.D.sup.27.1 1.5839                     (312) H                                                                                    ##STR218##         2 n.sub.D.sup.26.8 1.5519                     (313) H                                                                                    ##STR219##         2 n.sub.D.sup.25.4 1.5610                     (314) H                                                                                    ##STR220##         2 n.sub.D.sup.24.9 1.5941                     (315) H                                                                                    ##STR221##         2 n.sub.D.sup.25.0 1.5951                     (316) H                                                                                    ##STR222##         2 n.sup.25.3 1.5850                           (317) H                                                                                    ##STR223##         2 n.sub.D.sup.25.0 1.5680                     (318) H                                                                                    ##STR224##         2 n.sub.D.sup.25.0 1.6300                     (319) H                                                                                    ##STR225##         2 n.sub.D.sup.26.0 1.5661                     (320) H                                                                                    ##STR226##         2 m.p. 78.7° C.                        (321) H     n-C.sub.5 H.sub.11  2 n.sub.D.sup.23.7 1.4856                     (322) H     C(C.sub.2 H.sub.5)CHCH.sub.3                                                                      2 n.sub.D.sup.27.3 1.5021                     (323) H                                                                                    ##STR227##         2 n.sub.D.sup.27.0 1.4990                     (324) H                                                                                    ##STR228##         2 n.sub.D.sup.25.0 1.5620                     (325) H     CH.sub.2 OCH.sub.3  2 n.sub.D.sup.25.0 1.5029                     (326) H                                                                                    ##STR229##         2 n.sub.D.sup.25.2 1.5185                     (327) H                                                                                    ##STR230##         2 n.sub.D.sup.25.5 1.5560                     (328) H                                                                                    ##STR231##         2 n.sub.D.sup.25.8 1.6050                     (329) H                                                                                    ##STR232##         2 n.sub.D.sup.24.4 1.6121                     (330) H                                                                                    ##STR233##         2 n.sub.D.sup.24.0 1.5116                     (331) H                                                                                    ##STR234##         2 m.p. 140.3° C.                       (332) H                                                                                    ##STR235##         2 n.sub.D.sup.25.3 1.5110                     (333) H                                                                                    ##STR236##         2 n.sub.D.sup.25.3 1.5750                     (334) H                                                                                    ##STR237##         2 m.p. 95.6° C.                        (335) H                                                                                    ##STR238##         2 m.p. 97-100° C.                      (336) H                                                                                    ##STR239##         2 n.sub.D.sup.26.2 1.6123                     (337) H                                                                                    ##STR240##         2 n.sub.D.sup.24.5  1.5858                    (338) H                                                                                    ##STR241##         2 n.sup.25.2 1.5945                           (339) H                                                                                    ##STR242##         2 n.sub.D.sup.25.1 1.6070                     (340) H                                                                                    ##STR243##         1 n.sub.D.sup.24.0 1.5686                     (341) H                                                                                    ##STR244##         4 n.sub.D.sup.25.2 1.5600                     (342) H                                                                                    ##STR245##         2 n.sub.D.sup.27.5 1.5911                     (343) H                                                                                    ##STR246##         2 n.sub.D.sup.30.8 1.5688                     (344) CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                            2 C.A. 88, 49759k                             __________________________________________________________________________

Method (l):

When the present compound is the salt of the amine compound representedby the foregoing formula (V), provided that when both R⁶ and R⁷ are ahydrogen atom, salts with the following acids are excluded for eachvalue of n: when n is 1, hydrochloric acid, picric acid; when n is 2,hydrochloric acid, hydrobromic acid, phosphoric acid, methanesulfonicacid, ethanesulfonic acid, 2-hydroxyethanesulfonic acid,(2-cyclohexenylamino)methanesulfonic acid,(3-cyclohexenylamino)methanesulfonic acid, acetic acid, lactic acid,succinic acid, fumaric acid, maleic acid, malic acid, tartaric acid,citric acid, ascorbic acid, benzoic acid, salicylic acid, phenylaceticacid, mandelic acid, 4,4'-methylenebis(3-hydroxy-β-naphthoic acid); whenn is 3, hydrochloric acid; and when n is 4, picric acid, the presentcompound can be produced by reacting an amine compound represented bythe formula (V) with an acid of 0.95 to 1.0 equivalent based thereon at-10° to 80° C. for preferably 0.5 to 1 hour.

The acid described above includes for example inorganic acids, organicacids (e.g. organic sulfonic acids, organic sulfinic acids, organicphosphoric acids, substituted or non-substituted aliphatic, aromatic orheteroaromatic carboxylic acids, substituted or non-substitutedaliphatic polyhydric carboxylic acids or aromatic dicarboxylic acids,phenols and substituted or non-substituted dithiocarbamic acids, etc.),Lewis acids, etc.

More specifically, the inorganic acids include for example hydrochloricacid, hydrobromic acid, sulfuric acid, phosphoric acid, hydroiodic acid,hydrofluoric acid, sulfurous acid, nitric acid, nitrous acid,phosphorous acid, perchloric acid, chloric acid, chlorous acid, iodicacid, bromic acid, arsenic acid, carbonic acid, selenium hydride,tellurium hydride, phosphonic acid, hypophosphoric acid, diphosphonicacid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid,selenic acid, selenious acid, telluric acid, tellurous acid, arseniousacid, antimonic acid, antimonous acid, borofluoric acid, etc. Of theorganic acids, the organic sulfonic acids include for examplehydroxymethanesulfonic acid, trifluoromethanesulfonic acid,β-bromoethanesulfonic acid, allylsulfonic acid,2-methyl-2-[(1-propenyl)amino]-1-propanesulfonic acid,D-10-camphorsulfonic acid, benzenesulfonic acid, m-nitrobenzenesulfonicacid, m-benzenedisulfonic acid, methanesulfonic acid, ethanesulfonicacid, 2-hydroxyethanesulfonic acid, 2-(cyclohexenylamino)methanesulfonicacid, (3-cyclohexenylamino)methanesulfonic acid, p-ethylbenzenesulfonicacid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid,p-toluenesulfonic acid, p-chloromethylbenzenesulfonic acid,p-phenolsulfonic acid, 2-pyridylhydroxymethanesulfonic acid,2,6-naphthalenedisulfonic acid, etc.; the organic sulfinic acids includefor example benzenesulfinic acid, p-toluenesulfinic acid, etc.; theorganic phosphoric acids include for example phenylphosphonous acid,butylphosphonous acid, methylphosphonous acid, dibenzenephosphinic acid,dibutylphosphinic acid, benzenephosphonic acid, methylphosphonic acid,phenylphosphinic acid, methylphosphinic acid, dibenzenethiophosphinicacid, dibutylthiophosphinic acid, benzenethiophosphonic acid,methylthiophosphonic acid, phenylthiophosphinic acid,methylthiophosphinic acid, benzenethiophosphonous acid,dibutylthiophosphonous acid, diethyl dithiophosphate,α-hydroxybenzylphosphonous acid, toluenephosphonous acid, etc.; thesubstituted or non-substituted aliphatic carboxylic acids include forexample mandelic acid, acetic acid, lactic acid, ascorbic acid,phenylacetic acid, bromoacetic acid, trichloroacetic acid,chlorodifluoroacetic acid, thioacetic acid, glycolacetic acid, glyoxylicacid, acrylic acid, β-chloroacrylic acid, cyanoacetic acid, ethoxyaceticacid, β-chloropropionic acid, perfluoropropionic acid, propiolic acid,n-butyric acid, isobutyric acid, α-hydroxyisobutyric acid, crotonicacid, mucochloric acid, cyclopropanecarboxylic acid, isovaleric acid,1-methylcyclopropanecarboxylic acid, 1-cyanocyclopropanecarboxylic acid,cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 2-ketobutyricacid, levulinic acid, pivalic acid, tert-butylacetic acid, coumarinicacid, 3-cyclohexenecarboxylic acid, β-2-furylacrylic acid,3-pyridylacetic acid, phenylthioacetic acid, m-chlorophenylacetic acid,o-nitrophenylacetic acid, p-fluorophenylacetic acid,o-hydroxyphenylacetic acid, phenoxyacetic acid, o-chlorophenoxyaceticacid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid,cyclohexylacetic acid, 1-methyl-1-cyclohexanecarboxylic acid,6-acetamidohexanoic acid, heptylic acid, dl-terebic acid, benzoylformicacid, cinnamic acid, o-chlorocinnamic acid, 2,4-dichlorocinnamic acid,m-nitrocinnamic acid, o-hydroxycinnamic acid, dl-2-phenoxypropionicacid, 3-phenoxypropionic acid, 3-phenylpropionic acid,3-(p-hydroxyphenyl)propionic acid, 2-(2,4,5-trichlorophenoxy)propionicacid, 4-methoxyphenylacetic acid, p-chloro-2-methylphenylacetic acid,3,4-methylenedioxyphenylacetic acid, 4-chloro-2-methylphenoxyaceticacid, m-tolylacetic acid, α,α,α-trifluoro-m-tolylacetic acid,p-hydroxyphenylpyruvic acid, α-cyanocinnamic acid, p-methoxycinnamicacid, m-trifluoromethylcinnamic acid, 3,4-methylenedioxycinnamic acid,3,4-dimethoxyphenylacetic acid,(31)-α-methoxy-α-trifluoromethylphenylacetic acid,1,4-benzdioxane-6-acetic acid, 3-phenyl-n-butyric acid,1-phenyl-1-cyclopropanecarboxylic acid,2-(p-methoxyphenyl)-acetylene-1-carboxylic acid, 3-benzoylpropionicacid, 2-p-chlorophenoxy)-2-methylpropionic acid, α-naphthylacetic acid,β-naphthoxyacetic acid, 3,4,5-trimethoxyphenylacetic acid,diphenylacetic acid, bis(p-chlorophenyl)acetic acid, l-menthoxyaceticacid, diphenyleneacetic acid, 1-phenylcyclopentanecarboxylic acid,1-(p-chlorophenyl)-1-cyclopentanecarboxylic acid, dl-3-camphorcarboxylicacid, palmitic acid, stearic acid, benzilic acid, desoxycholic acid,linolic acid, oleic acid, α-acetamidocinnamic acid, etc.; the aromaticcarboxylic acids include for example benzoic acid, salicylic acid,o-toluic acid, α,α,α-trifluoro-m-toluic acid, p-ethylbenzoic acid,2,6-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid,p-tert-butylbenzoic acid, p-bromomethylbenzoic acid,2-biphenylcarboxylic acid, 4,4'-methylenebis(3-hydroxy-β-naphthoicacid), α-naphthoic acid, p-benzoylbenzoic acid, phthalamic acid,o-phthalaldehydic acid, m-nitrobenzoic acid, 3,4-dinitrobenzoic acid,m-cyanobenzoic acid, thiosalicylic acid, gallic acid, m-hydroxybenzoicacid, 2,3-dihydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, o-anisicacid, 3,4-dimethoxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid,4-hydroxy-3,5-dimethoxybenzoic acid, 4-n-butoxybenzoic acid,3-phenoxybenzoic acid, piperonylic acid, o-acetamidobenzoic acid,p-chlorobenzoic acid, 3,5-dichlorobenzoic acid, o-fluorobenzoic acid,m-fluorobenzoic acid, 2,6-difluorobenzoic acid, 2,6-dichlorobenzoicacid, 2,3,5-triiodobenzoic acid, 4-chlorosalicylic acid,3-nitrosalicylic acid, 5-bromosalicylic acid, 2-chloro-3-nitrobenzoicacid, 3-chloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoicacid, 3-chloro-4-methylbenzoic acid, 3-methoxy-4-nitrobenzoic acid,3-methoxy-4-hydroxybenzoic acid, 3-methoxy-4-methylbenzoic acid,3-methyl-2-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid,3,5-di-tert-butyl-4-hydroxybenzoic acid, o-thymotinic acid, etc.; theheteroaromatic carboxylic acids include for exampleN-methylpyrrole-2-carboxylic acid, 2-furancarboxylic acid,5-bromo-2-furancarboxylic acid, pyrrole-2-carboxylic acid,3-furancarboxylic acid, nicotinic acid, isonicotinic acid, citrazinicacid, α-picolinic acid, etc.; the substituted or non-substitutedaliphatic polyhydric carboxylic acids include for example succinic acid,fumaric acid, maleic acid, malic acid, tartaric acid, cittric acid,oxalic acid, malonic acid, ethylmalonic acid, hydroxymalonic acid,methylsuccinic acid, 2-methyl-2-phenylsuccinic acid,2-ethyl-2-methylsuccinic acid, 2-isopropylsuccinic acid, bromosuccinicacid, 2,3-dibromosuccinic acid, α-ketoglutaric acid,3-ethyl-3-methylglutaric acid, glutaconic acid, itaconic acid, mesaconicacid, citraconic acid, adipic acid, camphoric acid, diglycollic acid,acetylenedicarboxylic acid, dimethylcyclopropanedicarboxylic acid, etc.;the aromatic dicarboxylic acids include for example phthalic acid,isophthalic acid, terephthalic acid, homophthalic acid, 3-nitrophthalicacid, 4-hydroxyisophthalic acid, tetrachlorophthalic acid,tetrachloroterephthalic acid, nitroterephthalic acid,pyrazine-2,3-dicarboxylic acid, o-phenylenediacetic acid,5,5'-methylenedisalicylic acid, etc.; the phenols include for examplepicric acid, 2,4-dinitrophenol, 2,6-dinitrophenol,2,6-diiodo-4-nitrophenol, 2,6-dichloro-4-nitrophenol,2,5-dichloro-4-nitrophenol, 2,6-dibromo-4-nitrophenol,2-bromo-4-chloro-6-nitrophenol, 2,4-dichloro-6-nitrophenol, etc.; andthe substituted or non-substituted dithiocarbamic acids include forexample 2-cyclohexenyldithiocarbamic acid, 2-cycloheptenyldithiocarbamicacid, methyldithiocarbamic acid, dimethyldithiocarbamic acid,ethylenebis(dithiocarbamic acid), etc. Further, the Lewis acid includesfor example boron trifluoride, boron trichloride, boron tribromide,aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide,aluminum sulfate, iron fluoride, iron chloride, iron bromide, ironnitrate, iron sulfate, gallium fluoride, gallium chloride, antimonyfluoride, antimony chloride, antimony sulfate, indium fluoride, indiumchloride, tin fluoride, tin chloride, tin bromide, tin iodide, arsenicfluoride, arsenic chloride, zinc fluoride, zinc chloride, zinc bromide,zinc iodide, copper chloride, barium chloride, silver chloride, etc.

The solvent used in the foregoing method includes for example aliphatichydrocarbons such as hexane, heptane, ligroin, petroleum ether, etc.,aromatic hydrocarbons such as benzene, toluene, xylene, etc.,halogenated hydrocarbons such as chloroform, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers such asdiethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether, etc., ketones such as acetone, methyl ethylketone, methyl isobutyl ketone, isophorone, cyclohexanone, etc.,alcohols such as methanol, ethanol, isopropanol, tert-butanol, octanol,cyclohexanol, methyl cellosolve, diethylene glycol, glycerin, etc.,esters such as ethyl formate, ethyl acetate, butyl acetate, diethylcarbonate, etc., nitro compounds such as nitroethane, nitrobenzene,etc., nitriles such as acetonitrile, isobutyronitrile, etc., sulfurcompounds such as dimethyl sulfoxide, sulfolane, etc., water, andmixtures thereof.

Next, examples of production of the present compound by the method (l)will be shown.

Production example 17

Conc. hydrochloric acid (10.1 g) was added dropwise to a mixture of2-cycloheptenylamine (11.1 g, 0.1 mole) and isopropyl alcohol (24 g)with stirring and ice-cooling. The reaction mixture was concentratedunder reduced pressure, and the deposited crystal was washed withdiethyl ether and dried to obtain 14 g of 2-cycloheptenylaminehydrochloride [Compound (349)].

m.p. 174°-176° C.

Production example 18

To a solution of phenylphosphinic acid (0.72 g, 10 mmoles) in isopropylalcohol (2.4 g) was added dropwise 2-cycloheptenylamine (0.56 g, 10mmoles) with stirring and ice-cooling. The reaction mixture wasconcentrated under reduced pressure, and the deposited crystal waswashed with diethyl ether and dried to obtain 1.2 g of thephenylphosphinic acid salt of 2-cycloheptenylamine [Compound (353)].

m.p. 171°-174° C.

Some of the present compounds which can be produced by this method areshown in Table 5 by means of corresponding acids.

                                      TABLE 5                                     __________________________________________________________________________    Salts of the 2-cycloalkenylamine derivative represented by the formula,        ##STR247##                                                                   Compound                                                                      No.   R.sup.1                                                                          R.sup.2 n Acid         Physical constant                             __________________________________________________________________________    (345) H  CH.sub.3                                                                              3 Hydrochloric acid                                                                          m.p. 125° C.                           (346) H  H       1    --        C.A. 81,115149v                               (347) H  H       3    --        Ann. 317,243(1901)                            (348) H  H       4    --        C.A. 58,9005a                                 (349) H  H       3 Hydrochloric acid                                                                          Ann. 317,243(1901)                            (350) H  H       1 Hydrochloric acid                                                                          C.A. 56,2341b                                 (351) H  H       4 Hydrochloric acid                                                                          m.p. 271° C.                           (352) H  H       1 Picric acid  C.A. 56,2341b                                 (353) H  H       3 Phenylphosphinic acid                                                                      m.p. 171-174° C.                       (354) H  H       3 Methylphosphinic acid                                                                      n.sub.D.sup.23.4 1.4901                       (355) H  H       3 α-Naphthalenesulfonic acid                                                           n.sub.D.sup.23.4 1.5581                       (356) H  H       3 n-Butyric acid                                                                             n.sub.D.sup.23.4 1.4827                       (357) H  H       3 Zinc chloride                                                                              m.p. 137-144° C.                       (358) H  H       3 Ferric chloride                                                                            m.p. 137-140° C.(dec.)                 (359) H  H       3 p-Toluenesulfinic acid                                                                     m.p. 156-159° C.                       (360) H  H       3 3-Chloropropionic acid                                                                     m.p. 82-85° C.                         (361) H  H       3 Benzoic acid m.p. 167-170° C.                       (362) H  H       3 o-Anisic acid                                                                              m.p. 160-163° C.                       (363) H  H       3 2-Furancarboxylic acid                                                                     m.p. 187-190° C.                       (364) H  H       3 Maleic acid  m.p. 100-103° C.                       (365) H  H       3 Phthalic acid                                                                              m.p. 151-154° C.                       (366) H  H       1 2,4-Dinitrophenol                                                                          m.p. 164-166° C.                       (367) H  H       3 Acetic acid  m.p. 86° C.                            (368) H  H       3                                                                                ##STR248##  n.sub.D.sup.18.4 1.5076                       (369) H  CH(CH.sub.3)CN                                                                        3 Phenylphosphinic acid                                                                      m.p. 95° C.                            (370) H  CH(CH.sub.3)CN                                                                        3 Methylphosphinic acid                                                                      n.sub.D.sup.22.0 1.5000                       (371) H  CH.sub.2 CN                                                                           3 Phenylphosphinic acid                                                                      m.p. 77° C.                            (372) CH.sub.3                                                                         CH.sub.3                                                                              3 Hydrochloric acid                                                                          m.p. 159° C.                           (373) CH.sub.3                                                                         CH.sub.3                                                                              3 Phenylphosphinic acid                                                                      n.sub.D.sup.23.6 1.5389                       (374) CH.sub. 3                                                                        H       3 Phenylphosphinic acid                                                                      n.sub.D.sup.23.5 1.5400                       __________________________________________________________________________

When the present compounds thus obtained are used as the activeingredient of soil disease-controlling agents, they may be used as suchwithout adding any other components, but generally, they are formulatedinto emulsifiable concentrates, wettable powders, suspensionformulations, granules, dusts, water-soluble formulations, fine granulesand the like by mixing with solid carriers, liquid carriers, surfaceactive agents and other auxiliaries for formulation.

These formulations contain the present compound as an active ingredientin amounts of 0.1 to 99.9%, preferably 0.2 to 80.0% by weight ratio.

The above solid carrier includes for example the fine powders orgranules of kaolin clay, attapulgite clay, bentonite, terra abla,pyrophyllite, talc, diatomaceous earth, calcite, corn stalk powder,walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicondioxide, etc. The liquid carrier includes for example aromatichydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g.isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone,cyclohexanone, isophorone), vegetable oils (e.g. soybean oil, cottonseed oil), dimethyl sulfoxide, acetonitrile, water and the like.

As the surface active agent used for emulsification, dispersion,wetting, etc., there are given for examples anionic surface activeagents such as the salt of alkyl sulfate, alkyl(aryl) sulfonates,dialkyl sulfosuccinates, the salt of the phosphoric acid ester ofpolyoxyethylene alkylaryl ether, naphthalenesulfonic acid/formalincondensates, etc. and nonionic surface active agents such aspolyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene blockcopolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters, etc. The auxiliary for formulation includes for examplelignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC(carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

Next, formulation examples will be shown. The present compounds areshown by Compound No. in Tables 1 to 5. Parts in the examples are byweight.

Formulation example 1

Two parts of the compound (2), 88 parts of kaolin clay and 10 parts oftalc are thoroughly mixed while being powdered to obtain a dust.

Formulation example 2

Two parts of the compound (4), 1 part of synthetic hydrated silicondioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65parts of kaolin clay are thoroughly mixed while being powdered, wellkneaded with water, granulated and then dried to obtain a granule.

Formulation example 3

Fifty parts of the compound (123), 3 parts of calcium lignosulfonate, 2parts of sodium lauryl sulfate and 45 parts of synthetic hydratedsilicon dioxide are thoroughly mixed while being powdered to obtain awettable powder.

Formulation example 4

Ten parts of the compound (217), 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 30 partsof xylene and 40 parts of isopropanol are thoroughly mixed to obtain anemulsifiable concentrate.

Formulation example 5

Thirty parts of the compound (280) is dissolved in dimethyl sulfoxide,and the resulting solution is adsorbed in 70 parts of attapulgite clay.The clay impregnated with the solution is then dried to obtain a finegranule.

Formulation example 6

Ten parts of the compound (349), 1 part of polyoxyethylene styrylphenylether and 89 parts of water are mixed to obtain a water-solubleformulation.

These formulations, either as such or as aqueous dilute liquors, areused in foliar treatment or soil treatment. In the case of soiltreatment, the formulations are sprayed (or scattered) onto soil surface[as need arises, they are mixed with the soil after spraying (orscattering)], or the soil is drenched with them. Also, an increase inthe controlling effect can be expected by using them in mixture withother soil disease-controlling agents. Further, these formulations mayalso be used in mixture with other fungicides, soil insect pestcontrolling agents, nematocides, plant growth regulating agents,fertilizers, soil improvers and the like.

When the present compound is used as the active ingredient of soildisease controlling agents, its dosage rate is generally 0.001 to 50 kgper 10 ares, preferably 0.01 to 10 kg per 10 ares. The granule, dust,fine granule, etc. are used as such without dilution, and when theemulsifiable concentrate, wettable powder, suspension formuation,water-soluble formulation, etc. are used as aqueous dilute liquors,their application concentration is 0.0005 to to 5.0%, preferably 0.005to 0.5%.

Next, that the present compound is useful as the active ingredient ofsoil disease controlling agents will be illustrated with reference tothe following test examples. Hereupon, the present compounds are shownby Compound No. in Tables 1 to 5, and compounds used as a control areshown by Compound symbol in Table 6.

                  TABLE 6                                                         ______________________________________                                        Com-                                                                          pound                                                                         symbol                                                                              Chemical structure    Remark                                            ______________________________________                                               ##STR249##           Benomyl (commercial fungicide)                    B     CCl.sub.3 NO.sub.2    Chloropicrin                                                                  (commercial                                                                   fumigant)                                         C                                                                                    ##STR250##           Hydroxyisoxazole (commercial fungicide)           D                                                                                    ##STR251##           PCNB (commercial fungicide)                       ______________________________________                                    

The controlling effect is indicated by the numerical value of thepercentage of healthy seedlings obtained as follows: The condition ofdisease of test plants on examination, i.e. the degrees of the colonyand symptom on the leaves, stems, roots, etc. of the test plants areobserved with the naked eye; the number of test plants showing no colonynor symptom at all (hereinafter referred to as number of healthyseedlings) is counted for each case described below: A case wherein thecompound was applied (hereinafter referred to as number of healthyseedlings in treated plot) and another case wherein neither applicationof the compound nor inoculation of pathogens was carried out(hereinafter referred to as number of healthy seedlings in untreated anduninoculated plot); and the percentage of healthy seedlings (%) isobtained from the following equation:

TEST EXAMPLE 1

Controlling effect against yellows of Japanese radish (Fusariumoxysporum f.sp.raphani)

A plastic pot was filled with a well mixed soil of field soil andinfested soil containing cultured Fusarium oxysporum f.sp. raphani, andthe seed of radish (variety, Wase-40 nichi) was sowed at a rate of15/pot and covered with soil. Thereafter, a prescribed amount of eachtest compound in the form of wettable powder-formulated according toFormulation example 3 was diluted with water and applied to soildrenching. After three weeks' cultivation in a greenhouse, thecontrolling effect was examined.

The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                   Dosage rate of                                                                             Percentage of                                         Test       active ingre-                                                                              healthy seed-                                                                             Phyto-                                    compound   dient (g/10 are)                                                                           lings (%)   toxicity                                  ______________________________________                                         (1)       300          100.0       --                                         (2)       "            100.0       --                                         (3)       "            100.0       --                                         (4)       "            100.0       --                                         (5)       "            100.0       --                                         (6)       "            100.0       --                                         (7)       "            100.0       --                                         (8)       "            100.0       --                                         (9)       "            100.0       --                                         (10)      "            100.0       --                                         (11)      "            100.0       --                                         (12)      "            100.0       --                                         (13)      "            100.0       --                                         (14)      "            100.0       --                                         (15)      "            100.0       --                                         (16)      "            100.0       --                                         (17)      "            100.0       --                                         (18)      "            100.0       --                                         (19)      "            100.0       --                                         (20)      "            100.0       --                                         (21)      "            100.0       --                                         (22)      "            100.0       --                                         (23)      "            100.0       --                                         (24)      "            100.0       --                                         (25)      "            100.0       --                                         (26)      "            100.0       --                                         (27)      "            100.0       --                                         (28)      "            100.0       --                                         (29)      "            100.0       --                                         (30)      "            100.0       --                                         (31)      "            100.0       --                                         (32)      "            100.0       --                                         (33)      "            100.0       --                                         (34)      "            100.0       --                                         (35)      "            100.0       --                                         (36)      "            100.0       --                                         (37)      "            100.0       --                                         (38)      "            100.0       --                                         (39)      "            100.0       --                                         (40)      "            100.0       --                                         (41)      "            100.0       --                                         (42)      "            100.0       --                                         (43)      "            100.0       --                                         (44)      "            100.0       --                                         (45)      "            100.0       --                                         (46)      "            100.0       --                                         (47)      "            100.0       --                                         (48)      "            100.0       --                                         (49)      "            100.0       --                                         (50)      "            100.0       --                                         (51)      "            100.0       --                                         (52)      "            100.0       --                                         (53)      "            100.0       --                                         (54)      "            100.0       --                                         (55)      "            100.0       --                                         (56)      "            100.0       --                                         (57)      "            100.0       --                                         (58)      "            100.0       --                                         (59)      "            100.0       --                                         (60)      "            100.0       --                                         (61)      "            100.0       --                                         (62)      "            100.0       --                                         (63)      "            100.0       --                                         (64)      "            100.0       --                                         (65)      "            100.0       --                                         (66)      "            100.0       --                                         (67)      "            100.0       --                                         (68)      "            100.0       --                                         (69)      "            100.0       --                                         (70)      "            100.0       --                                         (71)      "            100.0       --                                         (72)      "            100.0       --                                         (73)      "            100.0       --                                         (74)      "            100.0       --                                         (75)      "            100.0       --                                         (76)      "            100.0       --                                         (77)      "            100.0       --                                         (78)      "            100.0       --                                         (79)      "            100.0       --                                         (80)      "            100.0       --                                          (81)     "            100.0       --                                         (82)      "            100.0       --                                         (83)      "            100.0       --                                         (84)      "            100.0       --                                         (85)      "            100.0       --                                         (86)      "            100.0       --                                         (87)      "            100.0       --                                         (88)      "            100.0       --                                         (89)      "            100.0       --                                         (90)      "            100.0       --                                         (91)      "            100.0       --                                         (92)      "            100.0       --                                         (93)      "            100.0       --                                         (94)      "            100.0       --                                         (95)      "            100.0       --                                         (96)      "            100.0       --                                         (97)      "            100.0       --                                         (98)      "            100.0       --                                         (99)      "            100.0       --                                        (100)      "            100.0       --                                        (101)      "            100.0       --                                        (102)      "            100.0       --                                        (103)      "            100.0       --                                        (104)      "            100.0       --                                        (105)      "            100.0       --                                        (106)      "            100.0       --                                        (107)      "            100.0       --                                        (108)      "            100.0       --                                        (109)      "            100.0       --                                        (110)      "            100.0       --                                        (111)      "            100.0       --                                        (112)      "            100.0       --                                        (113)      "            100.0       --                                        (114)      "            100.0       --                                        (115)      "            100.0       --                                        (116)      "            100.0       --                                        (117)      "            100.0       --                                        (118)      "            100.0       --                                        (119)      "            100.0       --                                        (120)      "            100.0       --                                        (121)      "            100.0       --                                        (122)      "            100.0       --                                        (123)      "            100.0       --                                        (124)      "            100.0       --                                        (125)      "            100.0       --                                        (126)      "            100.0       --                                        (127)      "            100.0       --                                        (128)      "            100.0       --                                        (129)      "            100.0       --                                        (130)      "            100.0       --                                        (131)      "            100.0       --                                        (132)      "            100.0       --                                        (133)      "            100.0       --                                        (134)      "            100.0       --                                        (135)      "            100.0       --                                        (136)      "            100.0       --                                        (137)      "            100.0       --                                        (138)      "            100.0       --                                        (139)      "            100.0       --                                        (140)      "            100.0       --                                        (141)      "            100.0       --                                        (142)      "            100.0       --                                        (143)      "            100.0       --                                        (144)      "            100.0       --                                        (145)      "            100.0       --                                        (146)      "            100.0       --                                        (147)      "            100.0       --                                        (148)      "            100.0       --                                        (149)      "            100.0       --                                        (150)      "            100.0       --                                        (151)      "            100.0       --                                        (152)      "            100.0       --                                        (153)      "            100.0       --                                        (154)      "            100.0       --                                        (155)      "            100.0       --                                        (156)      "            100.0       --                                        (157)      "            100.0       --                                        (158)      "            100.0       --                                        (159)      "            100.0       --                                        (160)      "            100.0       --                                        (161)      "            100.0       --                                        (162)      "            100.0       --                                        (163)      "            100.0       --                                        (164)      "            100.0       --                                        (165)      "            100.0       --                                        (166)      "            100.0       --                                        (167)      "            100.0       --                                        (168)      "            100.0       --                                        (169)      "            100.0       --                                        (170)      "            100.0       --                                        (171)      "            100.0       --                                        (172)      "            100.0       --                                        (173)      "            100.0       --                                        (174)      "            100.0       --                                        (175)      "            100.0       --                                        (176)      "            100.0       --                                        (177)      "            100.0       --                                        (178)      "            100.0       --                                        (179)      "            100.0       --                                        (180)      "            100.0       --                                        (181)      "            100.0       --                                        (182)      "            100.0       --                                        (183)      "            100.0       --                                        (184)      "            100.0       --                                        (185)      "            100.0       --                                        (186)      "            100.0       --                                        (187)      "            100.0       --                                        (188)      "            100.0       --                                        (189)      "            100.0       --                                        (190)      "            100.0       --                                        (191)      "            100.0       --                                        (192)      "            100.0       --                                        (193)      "            100.0       --                                        (194)      "            100.0       --                                        (195)      "            100.0       --                                        (196)      "            100.0       --                                        (197)      "            100.0       --                                        (198)      "            100.0       --                                        (199)      "            100.0       --                                        (200)      "            100.0       --                                        (201)      "            100.0       --                                        (202)      "            100.0       --                                        (203)      "            100.0       --                                        (204)      "            100.0       --                                        (205)      "            100.0       --                                        (206)      "            100.0       --                                        (207)      "            100.0       --                                        (208)      "            100.0       --                                        (209)      "            100.0       --                                        (210)      "            100.0       --                                        (211)      "            100.0       --                                        (212)      "            100.0       --                                        (213)      "            100.0       --                                        (214)      "            100.0       --                                        (215)      "            100.0       --                                        (216)      "            100.0       --                                        (217)      "            100.0       --                                        (218)      "            100.0       --                                        (219)      "            100.0       --                                        (220)      "            100.0       --                                        (221)      "            100.0       --                                        (222)      "            100.0       --                                        (223)      "            100.0       --                                        (224)      "            100.0       --                                        (225)      "            100.0       --                                        (226)      "            100.0       --                                        (227)      "            100.0       --                                        (228)      "            100.0       --                                        (229)      "            100.0       --                                        (230)      "            100.0       --                                        (231)      "            100.0       --                                        (232)      "            100.0       --                                        (233)      "            100.0       --                                        (234)      "            100.0       --                                        (235)      "            100.0       --                                        (236)      "            100.0       --                                        (237)      "            100.0       --                                        (238)      "            100.0       --                                        (239)      "            100.0       --                                        (240)      "            100.0       --                                        (241)      "            100.0       --                                        (242)      "            100.0       --                                        (243)      "            100.0       --                                        (244)      "            100.0       --                                        (245)      "            100.0       --                                        (246)      "            100.0       --                                        (247)      "            100.0       --                                        (248)      "            100.0       --                                        (249)      "            100.0       --                                        (250)      "            100.0       --                                        (251)      "            100.0       --                                        (252)      "            100.0       --                                        (253)      "            100.0       --                                        (254)      "            100.0       --                                        (255)      "            100.0       --                                        (256)      "            100.0       --                                        (257)      "            100.0       --                                        (258)      "            100.0       --                                        (259)      "            100.0       --                                        (260)      "            100.0       --                                        (261)      "            100.0       --                                        (262)      "            100.0       --                                        (263)      "            100.0       --                                        (264)      "            100.0       --                                        (265)      "            100.0       --                                        (266)      "            100.0       --                                        (267)      "            100.0       --                                        (268)      "            100.0       --                                        (269)      "            100.0       --                                        (270)      "            100.0       --                                        (271)      "            100.0       --                                        (272)      "            100.0       --                                        (273)      "            100.0       --                                        (274)      "            100.0       --                                        (275)      "            100.0       --                                        (276)      "            100.0       --                                        (277)      "            100.0       --                                        (278)      "            100.0       --                                        (279)      "            100.0       --                                        (280)      "            100.0       --                                        (281)      "            100.0       --                                        (282)      "            100.0       --                                        (283)      "            100.0       --                                        (284)      "            100.0       --                                        (285)      "            100.0       --                                        (286)      "            100.0       --                                        (287)      "            100.0       --                                        (288)      "            100.0       --                                        (289)      "            100.0       --                                        (290)      "            100.0       --                                        (291)      "            100.0       --                                        (292)      "            100.0       --                                        (293)      "            100.0       --                                        (294)      "            100.0       --                                        (295)      "            100.0       --                                        (296)      "            100.0       --                                        (297)      "            100.0       --                                        (298)      "            100.0       --                                        (299)      "            100.0       --                                        (300)      "            100.0       --                                        (301)      "            100.0       --                                        (302)      "            100.0       --                                        (303)      "            100.0       --                                        (304)      "            100.0       --                                        (305)      "            100.0       --                                        (306)      "            100.0       --                                        (307)      "            100.0       --                                        (308)      "            100.0       --                                        (309)      "            100.0       --                                        (310)      "            100.0       --                                        (311)      "            100.0       --                                        (312)      "            100.0       --                                        (313)      "            100.0       --                                        (314)      "            100.0       --                                        (315)      "            100.0       --                                        (316)      "            100.0       --                                        (317)      "            100.0       --                                        (318)      "            100.0       --                                        (319)      "            100.0       --                                        (320)      "            100.0       --                                        (321)      "            100.0       --                                        (322)      "            100.0       --                                        (323)      "            100.0       --                                        (324)      "            100.0       --                                        (325)      "            100.0       --                                        (326)      "            100.0       --                                        (327)      "            100.0       --                                        (328)      "            100.0       --                                        (329)      "            100.0       --                                        (330)      "            100.0       --                                        (331)      "            100.0       --                                        (332)      "            100.0       --                                        (333)      "            100.0       --                                        (334)      "            100.0       --                                        (335)      "            100.0       --                                        (336)      "            100.0       --                                        (337)      "            100.0       --                                        (338)      "            100.0       --                                        (339)      "            100.0       --                                        (340)      "            100.0       --                                        (341)      "            100.0       --                                        (342)      "            100.0       --                                        (343)      "            100.0       --                                        (344)      "            100.0       --                                        (345)      "            100.0       --                                        (346)      "            100.0       --                                        (347)      "            100.0       --                                        (348)      "            100.0       --                                        (349)      "            100.0       --                                        (350)      "            100.0       --                                        (351)      "            100.0       --                                        (352)      "            100.0       --                                        (353)      "            100.0       --                                        (354)      "            100.0       --                                        (355)      "            100.0       --                                        (356)      "            100.0       --                                        (357)      "            100.0       --                                        (358)      "            100.0       --                                        (359)      "            100.0       --                                        (360)      "            100.0       --                                        (361)      "            100.0       --                                        (362)      "            100.0       --                                        (363)      "            100.0       --                                        (364)      "            100.0       --                                        (365)      "            100.0       --                                        (366)      "            100.0       --                                        (367)      "            100.0       --                                        (368)      "            100.0       --                                        (369)      "            100.0       --                                        (370)      "            100.0       --                                        (371)      "            100.0       --                                        (372)      "            100.0       --                                        (373)      "            100.0       --                                        (374)      "            100.0       --                                        A          600           57.8       --                                        Inoculated and                                                                           --            8.9        --                                        untreated plot                                                                Uninoculated and                                                                         --           100.0       --                                        untreated plot                                                                ______________________________________                                    

TEST EXAMPLE 2

Controlling effect against yellows of cabbage (Fusarium oxysporumf.sp.conglutinans)

A plastic pot was filled with a uniform mixture of field soil, infestedsoil containing cultured Fusarium oxysporum f.sp. conglutinans and aprescribed amount of each test compound in the form of fine granuleformulated according to Formulation example 5. In this test,chloropicrin was used as follows: After the field soil and infested soilwere well mixed and filled in the plastic pot, a prescribed amount ofchloropicrin was injected into the soil which was then covered with apolyvinyl chloride film and allowed to stand for one week; thereafterthe film was removed and gas release was carried out for one week. Theseed of cabbage (variety, Shikidori) was sowed at a rate of 10/pot andcovered with soil. After three weeks' cultivation in a greenhouse, thecontrolling effect was examined.

The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                                  Dosage rate of                                                                             Percentage of                                          Test      active ingre-                                                                              healthy seed-                                                                              Phyto-                                    compound  dient (g/10 are)                                                                           lings (%)    toxicity                                  ______________________________________                                        (1)       300          100.0        --                                        (2)       "            100.0        --                                        (3)       "            100.0        --                                        (4)       "            100.0        --                                        (5)       "            100.0        --                                        (6)       "            100.0        --                                        (7)       "            100.0        --                                        (8)       "            100.0        --                                        (9)       "            100.0        --                                        (10)      "            100.0        --                                        (11)      "            100.0        --                                        (12)      "            100.0        --                                        (13)      "            100.0        --                                        (14)      "            100.0        --                                        (15)      "            100.0        --                                        (16)      "            100.0        --                                        (17)      "            100.0        --                                        (18)      "            100.0        --                                        (19)      "            100.0        --                                        (20)      "            100.0        --                                        (21)      "            100.0        --                                        (22)      "            100.0        --                                        (23)      "            100.0        --                                        (24)      "            100.0        --                                        (25)      "            100.0        --                                        (26)      "            100.0        --                                        (27)      "            100.0        --                                        (28)      "            100.0        --                                        (29)      "            100.0        --                                        (30)      "            100.0        --                                        (31)      "            100.0        --                                        (32)      "            100.0        --                                        (33)      "            100.0        --                                        (34)      "            100.0        --                                        (35)      "            100.0        --                                        (36)      "            100.0        --                                        (37)      "            100.0        --                                        (38)      "            100.0        --                                        (39)      "            100.0        --                                        (40)      "            100.0        --                                        (41)      "            100.0        --                                        (42)      "            100.0        --                                        (43)      "            100.0        --                                        (44)      "            100.0        --                                        (45)      "            100.0        --                                        (46)      "            100.0        --                                        (47)      "            100.0        --                                        (48)      "            100.0        --                                        (49)      "            100.0        --                                        (50)      "            100.0        --                                        (51)      "            100.0        --                                        (52)      "            100.0        --                                        (53)      "            100.0        --                                        (54)      "            100.0        --                                        (55)      "            100.0        --                                        (56)      "            100.0        --                                        (57)      "            100.0        --                                        (58)      "            100.0        --                                        (59)      "            100.0        --                                        (60)      "            100.0        --                                        (61)      "            100.0        --                                        (62)      "            100.0        --                                        (63)      "            100.0        --                                        (64)      "            100.0        --                                        (65)      "            100.0        --                                        (66)      "            100.0        --                                        (67)      "            100.0        --                                        (68)      "            100.0        --                                        (69)      "            100.0        --                                        (70)      "            100.0        --                                        (71)      "            100.0        --                                        (72)      "            100.0        --                                        (73)      "            100.0        --                                        (74)      "            100.0        --                                        (75)      "            100.0        --                                        (76)      "            100.0        --                                        (77)      "            100.0        --                                        (78)      "            100.0        --                                        (79)      "            100.0        --                                        (80)      "            100.0        --                                        (81)      "            100.0        --                                        (82)      "            100.0        --                                        (83)      "            100.0        --                                        (84)      "            100.0        --                                        (85)      "            100.0        --                                        (86)      "            100.0        --                                        (87)      "            100.0        --                                        (88)      "            100.0        --                                        (89)      "            100.0        --                                        (90)      "            100.0        --                                        (91)      "            100.0        --                                        (92)      "            100.0        --                                        (93)      "            100.0        --                                        (94)      "            100.0        --                                        (95)      "            100.0        --                                        (96)      "            100.0        --                                        (97)      "            100.0        --                                        (98)      "            100.0        --                                        (99)      "            100.0        --                                        (100)     "            100.0        --                                        (101)     "            100.0        --                                        (102)     "            100.0        --                                        (103)     "            100.0        --                                        (104)     "            100.0        --                                        (105)     "            100.0        --                                        (106)     "            100.0        --                                        (107)     "            100.0        --                                        (108)     "            100.0        --                                        (109)     "            100.0        --                                        (110)     "            100.0        --                                        (111)     "            100.0        --                                        (112)     "            100.0        --                                        (113)     "            100.0        --                                        (114)     "            100.0        --                                        (115)     "            100.0        --                                        (116)     "            100.0        --                                        (117)     "            100.0        --                                        (118)     "            100.0        --                                        (119)     "            100.0        --                                        (120)     "            100.0        --                                        (121)     "            100.0        --                                        (122)     "            100.0        --                                        (123)     "            100.0        --                                        (124)     "            100.0        --                                        (125)     "            100.0        --                                        (126)     "            100.0        --                                        (127)     "            100.0        --                                        (128)     "            100.0        --                                        (129)     "            100.0        --                                        (130)     "            100.0        --                                        (131)     "            100.0        --                                        (132)     "            100.0        --                                        (133)     "            100.0        --                                        (134)     "            100.0        --                                        (135)     "            100.0        --                                        (136)     "            100.0        --                                        (137)     "            100.0        --                                        (138)     "            100.0        --                                        (139)     "            100.0        --                                        (140)     "            100.0        --                                        (141)     "            100.0        --                                        (142)     "            100.0        --                                        (143)     "            100.0        --                                        (144)     "            100.0        --                                        (145)     "            100.0        --                                        (146)     "            100.0        --                                        (147)     "            100.0        --                                        (148)     "            100.0        --                                        (149)     "            100.0        --                                        (150)     "            100.0        --                                        (151)     "            100.0        --                                        (152)     "            100.0        --                                        (153)     "            100.0        --                                        (154)     "            100.0        --                                        (155)     "            100.0        --                                        (156)     "            100.0        --                                        (157)     "            100.0        --                                        (158)     "            100.0        --                                        (159)     "            100.0        --                                        (160)     "            100.0        --                                        (161)     "            100.0        --                                        (162)     "            100.0        --                                        (163)     "            100.0        --                                        (164)     "            100.0        --                                        (165)     "            100.0        --                                        (166)     "            100.0        --                                        (167)     "            100.0        --                                        (168)     "            100.0        --                                        (169)     "            100.0        --                                        (170)     "            100.0        --                                        (171)     "            100.0        --                                        (172)     "            100.0        --                                        (173)     "            100.0        --                                        (174)     "            100.0        --                                        (175)     "            100.0        --                                        (176)     "            100.0        --                                        (177)     "            100.0        --                                        (178)     "            100.0        --                                        (179)     "            100.0        --                                        (180)     "            100.0        --                                        (181)     "            100.0        --                                        (182)     "            100.0        --                                        (183)     "            100.0        --                                        (184)     "            100.0        --                                        (185)     "            100.0        --                                        (186)     "            100.0        --                                        (187)     "            100.0        --                                        (188)     "            100.0        --                                        (189)     "            100.0        --                                        (190)     "            100.0        --                                        (191)     "            100.0        --                                        (192)     "            100.0        --                                        (193)     "            100.0        --                                        (194)     "            100.0        --                                        (195)     "            100.0        --                                        (196)     "            100.0        --                                        (197)     "            100.0        --                                        (198)     "            100.0        --                                        (199)     "            100.0        --                                        (200)     "            100.0        --                                        (201)     "            100.0        --                                        (202)     "            100.0        --                                        (203)     "            100.0        --                                        (204)     "            100.0        --                                        (205)     "            100.0        --                                        (206)     "            100.0        --                                        (207)     "            100.0        --                                        (208)     "            100.0        --                                        (209)     "            100.0        --                                        (210)     "            100.0        --                                        (211)     "            100.0        --                                        (212)     "            100.0        --                                        (213)     "            100.0        --                                        (214)     "            100.0        --                                        (215)     "            100.0        --                                        (216)     "            100.0        --                                        (217)     "            100.0        --                                        (218)     "            100.0        --                                        (219)     "            100.0        --                                        (220)     "            100.0        --                                        (221)     "            100.0        --                                        (222)     "            100.0        --                                        (223)     "            100.0        --                                        (224)     "            100.0        --                                        (225)     "            100.0        --                                        (226)     "            100.0        --                                        (227)     "            100.0        --                                        (228)     "            100.0        --                                        (229)     "            100.0        --                                        (230)     "            100.0        --                                        (231)     "            100.0        --                                        (232)     "            100.0        --                                        (233)     "            100.0        --                                        (234)     "            100.0        --                                        (235)     "            100.0        --                                        (236)     "            100.0        --                                        (237)     "            100.0        --                                        (238)     "            100.0        --                                        (239)     "            100.0        --                                        (240)     "            100.0        --                                        (241)     "            100.0        --                                        (242)     "            100.0        --                                        (243)     "            100.0        --                                        (244)     "            100.0        --                                        (245)     "            100.0        --                                        (246)     "            100.0        --                                        (247)     "            100.0        --                                        (248)     "            100.0        --                                        (249)     "            100.0        --                                        (250)     "            100.0        --                                        (251)     "            100.0        --                                        (252)     "            100.0        --                                        (253)     "            100.0        --                                        (254)     "            100.0        --                                        (255)     "            100.0        --                                        (256)     "            100.0        --                                        (257)     "            100.0        --                                        (258)     "            100.0        --                                        (259)     "            100.0        --                                        (260)     "            100.0        --                                        (261)     "            100.0        --                                        (262)     "            100.0        --                                        (263)     "            100.0        --                                        (264)     "            100.0        --                                        (265)     "            100.0        --                                        (266)     "            100.0        --                                        (267)     "            100.0        --                                        (268)     "            100.0        --                                        (269)     "            100.0        --                                        (270)     "            100.0        --                                        (271)     "            100.0        --                                        (272)     "            100.0        --                                        (273)     "            100.0        --                                        (274)     "            100.0        --                                        (275)     "            100.0        --                                        (276)     "            100.0        --                                        (277)     "            100.0        --                                        (278)     "            100.0        --                                        (279)     "            100.0        --                                        (280)     "            100.0        --                                        (281)     "            100.0        --                                        (282)     "            100.0        --                                        (283)     "            100.0        --                                        (284)     "            100.0        --                                        (285)     "            100.0        --                                        (286)     "            100.0        --                                        (287)     "            100.0        --                                        (288)     "            100.0        --                                        (289)     "            100.0        --                                        (290)     "            100.0        --                                        (291)     "            100.0        --                                        (292)     "            100.0        --                                        (293)     "            100.0        --                                        (294)     "            100.0        --                                        (295)     "            100.0        --                                        (296)     "            100.0        --                                        (297)     "            100.0        --                                        (298)     "            100.0        --                                        (299)     "            100.0        --                                        (300)     "            100.0        --                                        (301)     "            100.0        --                                        (302)     "            100.0        --                                        (303)     "            100.0        --                                        (304)     "            100.0        --                                        (305)     "            100.0        --                                        (306)     "            100.0        --                                        (307)     "            100.0        --                                        (308)     "            100.0        --                                        (309)     "            100.0        --                                        (310)     "            100.0        --                                        (311)     "            100.0        --                                        (312)     "            100.0        --                                        (313)     "            100.0        --                                        (314)     "            100.0        --                                        (315)     "            100.0        --                                        (316)     "            100.0        --                                        (317)     "            100.0        --                                        (318)     "            100.0        --                                        (319)     "            100.0        --                                        (320)     "            100.0        --                                        (321)     "            100.0        --                                        (322)     "            100.0        --                                        (323)     "            100.0        --                                        (324)     "            100.0        --                                        (325)     "            100.0        --                                        (326)     "            100.0        --                                        (327)     "            100.0        --                                        (328)     "            100.0        --                                        (329)     "            100.0        --                                        (330)     "            100.0        --                                        (331)     "            100.0        --                                        (332)     "            100.0        --                                        (333)     "            100.0        --                                        (334)     "            100.0        --                                        (335)     "            100.0        --                                        (336)     "            100.0        --                                        (337)     "            100.0        --                                        (338)     "            100.0        --                                        (339)     "            100.0        --                                        (340)     "            100.0        --                                        (341)     "            100.0        --                                        (342)     "            100.0        --                                        (343)     "            100.0        --                                        (344)     "            100.0        --                                        (345)     "            100.0        --                                        (346)     "            100.0        --                                        (347)     "            100.0        --                                        (348)     "            100.0        --                                        (349)     "            100.0        --                                        (350)     "            100.0        --                                        (351)     "            100.0        --                                        (352)     "            100.0        --                                        (353)     "            100.0        --                                        (354)     "            100.0        --                                        (355)     "            100.0        --                                        (356)     "            100.0        --                                        (357)     "            100.0        --                                        (358)     "            100.0        --                                        (359)     "            100.0        --                                        (360)     "            100.0        --                                        (361)     "            100.0        --                                        (362)     "            100.0        --                                        (363)     "            100.0        --                                        (364)     "            100.0        --                                        (365)     "            100.0        --                                        (366)     "            100.0        --                                        (367)     "            100.0        --                                        (368)     "            100.0        --                                        (369)     "            100.0        --                                        (370)     "            100.0        --                                        (371)     "            100.0        --                                        (372)     "            100.0        --                                        (373)     "            100.0        --                                        (374)     "            100.0        --                                        B         15.0 (l/10 a)                                                                              73.3         --                                        Inoculated and                                                                          --           6.7          --                                        untreated plot                                                                Uninoculated                                                                            --           100.0        --                                        and untreated                                                                 plot                                                                          ______________________________________                                    

TEST EXAMPLE 3

Controlling effect against fusarium wilt of cucumber (Fusarium oxysporumf.sp. cucumerinum)

A plastic pot was filled with field soil and then with a uniform mixtureof infested soil containing cultured Fusarium oxysporum f.sp.cucumerinum and a prescribed amount of each test compound in the form ofdust prepared according to Formulation example 1 until the upper surfaceof the soil reached a level of 5 cm. In this test, as tohydroxyisoxazole, its prescribed amount was diluted with water andapplied to drench the pot filled with the field soil. The seed ofcucumber (variety, Shimoshirazuchibai) was sowed at a rate of 10/pot andcovered with soil. After three weeks' cultivation in a greenhouse, thecontrolling effect was examined.

The results are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                                   Dosage rate of                                                                             Percentage                                            Test       active ingre-                                                                              of healthy Phyto-                                     compound   dient (g/10 are)                                                                           seedlings (%)                                                                            toxicity                                   ______________________________________                                         (2)       300          100.0      --                                          (4)       "            100.0      --                                          (5)       "            100.0      --                                          (61)      "            100.0      --                                         (123)      "            100.0      --                                         (217)      "            100.0      --                                         (221)      "            100.0      --                                         (280)      "            100.0      --                                         (349)      "            100.0      --                                         (353)      "            100.0      --                                         C          600           53.3      --                                         Inoculated and                                                                           --            3.3       --                                         untreated plot                                                                Uninoculated and                                                                         --           100.0      --                                         untreated plot                                                                ______________________________________                                    

TEST EXAMPLE 4

Controlling effect against fusarium wilt of tomato (Fusarium oxysporumf.sp. lycopersici)

Each test compound in the form of emulsifiable concentrate formulatedaccording to Formulation example 4 was diluted with water to aprescribed concentration and sprayed on tomato seedlings (variety,Fukuju No. 2) in the three-leaf stage cultivated in a plastic pot sothat the spray liquor was thoroughly attached to the leaf surface. Afterspraying, the seedlings were inoculated by drenching their root with thespore suspension of Fusarium oxysporum f.sp. lycopersici. Afterinoculation, the seedlings were cultivated for three weeks in agreenhouse, and the controlling effect was examined.

The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                   Dosage rate of                                                                             Percentage                                            Test       active ingre-                                                                              of healthy Phyto-                                     compound   dient (g/10 are)                                                                           seedlings (%)                                                                            toxicity                                   ______________________________________                                         (2)       1000         100.0      --                                          (4)       "            100.0      --                                          (5)       "            100.0      --                                          (52)      "            100.0      --                                          (61)      "            100.0      --                                          (91)      "            100.0      --                                         (123)      "            100.0      --                                         (217)      "            100.0      --                                         (221)      "            100.0      --                                         (280)      "            100.0      --                                         (349)      "            100.0      --                                         (353)      "            100.0      --                                         (367)      "            100.0      --                                         A          "             53.3      --                                         Inoculated and                                                                           --            13.3      --                                         untreated plot                                                                Uninoculated and                                                                         --           100.0      --                                         untreated plot                                                                ______________________________________                                    

TEST EXAMPLE 5

Controlling effect against verticillium wilt of eggplant (Verticilliumalbo-atrum)

Soil in a plot (2 m²) was inoculated with 100 g of a wheat bran mediumcontaining cultured Verticillium albo-atrum, and then mixed with aprescribed amount of each test compound in the form of fine granuleformulated according to Formulation example 5. In this test,chloropicrin was used as follows: After inoculation with the pathogen, aprescribed amount of chloropicrin was injected into the soil which wasthen covered with a polyvinyl chloride film and allowed to stand for oneweek; thereafter, the film was removed, the soil was ploughed and gasrelease was carried out for further one week. Thereafter, an eggplantseedling (variety, Senryo No. 2) in the two-leaf stage was transplantedat a rate of 16/plot and cultivated for about six seeks in a greenhouse,and the controlling effect was examined.

The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                                   Dosage rate of                                                                             Percentage                                            Test       active ingre-                                                                              of healthy Phyto-                                     compound   dient (g/10 are)                                                                           seedlings (%)                                                                            toxicity                                   ______________________________________                                         (2)       1000         93.8       --                                          (4)       "            97.9       --                                          (5)       "            93.8       --                                          (60)      "            95.8       --                                          (61)      "            91.7       --                                         (123)      "            92.1       --                                         (289)      "            96.6       --                                         (217)      "            92.1       --                                         (221)      "            94.3       --                                         (349)      "            90.8       --                                         B          30.0 (l/10 a)                                                                              54.2       --                                         Inoculated and                                                                           --           10.4       --                                         untreated plot                                                                Uninoculated and                                                                         --           100.0      --                                         untreated plot                                                                ______________________________________                                    

TEST EXAMPLE 6

Controlling effect against club-root of chinese cabbage (Plasmodiophorabrassicae)

A plastic pot was filled with field soil and then with a uniform mixtureof a soil infested with Plasmodiophora brassicae and a prescribed amountof each test compound in the form of dust formulated according toFormulation example 1 until the upper surface of the soil reached alevel of 5 cm. Thereafter, the seed of chinese cabbage (variety,Taibyo-60 nichi) was sowed at a rate of 15/pot and covered with soil.After four weeks' cultivation in a greenhouse, the controlling effectwas examined.

The results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                                   Dosage rate of                                                                             Percentage                                            Test       active ingre-                                                                              of healthy Phyto-                                     compound   dient (g/10 are)                                                                           seedlings (%)                                                                            toxicity                                   ______________________________________                                         (2)       1000         93.8       --                                          (4)       "            93.8       --                                          (5)       "            83.3       --                                          (52)      "            85.4       --                                          (61)      "            89.6       --                                          (91)      "            92.1       --                                         (123)      "            81.6       --                                         (217)      "            83.9       --                                         (219)      "            87.5       --                                         (220)      "            91.3       --                                         (221)      "            89.7       --                                         (279)      "            81.2       --                                         (349)      "            85.2       --                                         (353)      "            90.4       --                                         D          2000         72.9       --                                         Inoculated and                                                                           --            8.9       --                                         untreated plot                                                                Uninoculated and                                                                         --           100.0      --                                         untreated plot                                                                ______________________________________                                    

TEST EXAMPLE 7

Controlling effect against fusarium wilt of cotton (Fusarium oxysporumf.sp. vasinfectum)

A plastic pot was filled with field soil and infested soil containingcultured Fusarium oxysporum f.sp. vasinfectum, and the seed of cotton(variety, Coker) dressed with a prescribed amount of each test compoundin the form of wettable powder formulated according to Formulationexample 3 was sowed at a rate of 10/pot and covered with soil. Afterthree weeks' cultivation in a greenhouse, the controlling effect wasexamined.

The results are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                                   Amount of active                                                                            Percentage                                           Test       ingredient/weight                                                                           of healthy Phyto-                                    compound   of dry seed (g/kg)                                                                          seedlings (%)                                                                            toxicity                                  ______________________________________                                         (91)      4             100.0      --                                        (217)      "             100.0      --                                        (219)      "             100.0      --                                        (221)      "             100.0      --                                        (247)      "             100.0      --                                        Inoculated and                                                                           --             9.7       --                                        untreated plot                                                                Uninoculated and                                                                         --            100.0      --                                        untreated plot                                                                ______________________________________                                    

What is claimed is:
 1. A 2-cycloalkenylamine derivative represented bythe formula, ##STR252## wherein X and Y, which may be the same ordifferent, represent an oxygen or sulfur atom and Z represents:a halosubstituted C₂ -C₃ alkenylene group and n represents 1, 2, 3 or
 4. 2.The compound according to claim 1 which isN-(2-cyclohepten-1-yl)-2,3-dichloromaleimide.